KR102115330B1 - Resist composition - Google Patents

Abstract

In the resist composition of the present invention, in a resist composition comprising a resist substrate and a solvent, the resist substrate contains a specific stereoisomer and the proportion of the specific stereoisomer occupied by the resist substrate is 50 to 100% by mass. to be.

Description

Resist composition {RESIST COMPOSITION}

The present invention relates to a resist composition containing a specific stereoisomer and a method for producing a resist pattern.

The conventional resist material so far is a polymer-based resist material capable of forming an amorphous thin film. For example, ultraviolet rays, far ultraviolet rays, and electron beams are applied to a resist thin film produced by applying a solution of a polymer-based resist material such as polymethyl methacrylate, polyhydroxystyrene or polyalkyl methacrylate having an acid dissociation reactor on a substrate. , By irradiating extreme ultraviolet (EUV), X-ray, and the like, a line pattern of about 45 to 100 nm is formed.

However, the polymer-based resist material has a molecular weight of about 10,000 to 100,000 and a large molecular weight distribution. Accordingly, in lithography using a polymer-based resist material, roughness occurs on the surface of the fine pattern, making it difficult to control the pattern dimension, and the yield decreases. Therefore, there is a limit to the refinement of the pattern in lithography using a conventional polymer-based resist material. Therefore, in order to produce a finer pattern, various low molecular weight resist materials have been proposed.

As a candidate for a low molecular weight resist material, for example, an alkali-type negative radiation composition using a low molecular weight polynuclear polyphenol compound as a main component (for example, see Patent Documents 1 and 2) has been proposed.

In addition, as a candidate for other low molecular weight resist materials, for example, an alkali-type negative radiation composition using a low molecular weight cyclic polyphenol compound as a main component (for example, refer to Patent Document 3 and Non-Patent Document 1). Is proposed.

Japanese Patent Publication No. 2005-326838 Japanese Patent Publication 2008-145539 Japanese Patent Publication 2009-173623

T.Nakayama, M.Nomura, K.Haga, M.Ueda: Bull.Chem.Soc.Jpn., 71,2979 (1998)

However, the negative radiation-sensitive compositions described in Patent Documents 1 and 2 do not have sufficient heat resistance, and the shape of the resulting resist pattern may be deteriorated.

Moreover, since the low molecular weight cyclic polyphenol compounds described in Patent Literature 3 and Non-Patent Literature 1 have a low molecular weight, it is expected to provide a resist pattern having a small molecular size, high resolution, and low roughness. Moreover, this low-molecular-weight cyclic polyphenol compound has a rigid cyclic structure in its skeleton, thereby giving high molecular weight and high heat resistance.

However, currently known low-molecular-weight cyclic polyphenol compounds have low solubility in a safety solvent used in semiconductor manufacturing processes, and, in addition, an alkali-type negative radiation composition using the low-molecular-weight cyclic polyphenol compound as a main component is , The sensitivity may be low, and the shape of the resulting resist pattern may be deteriorated. Therefore, improvement of a low molecular weight cyclic polyphenol compound is required. In addition, although the low molecular weight cyclic phenol compound described in Patent Document 3 has a good shape resist pattern, material properties such as solubility characteristics are slightly unstable, and a good shape resist pattern cannot be stably obtained.

Accordingly, an object of the present invention is to provide a resist composition that is highly sensitive, has a small roughness, and stably provides a resist pattern of good shape.

The present inventors have studied in order to solve the above problems, and as a result, have found a specific stereoisomer having a significantly improved solubility in a safety solvent. Further, it was found that the resist composition using this specific stereoisomer as an acid-amplified low-molecular-based resist substrate is surprisingly high-sensitivity, has a small roughness, and stably provides a resist pattern of a better shape, leading to the present invention.

That is, the present invention is as follows.

1.A resist composition comprising a resist substrate and a solvent,

A resist composition in which the resist substrate contains a compound represented by the following formula (1), and the proportion of the compound represented by the following formula (1) to the resist substrate is 50 to 100% by mass.

[Formula 1]

(In formula (1), R is each independently a hydrogen atom, a substituted or unsubstituted heterocyclic group, a halogen atom, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted 3 to 20 carbon atoms. Branched aliphatic hydrocarbon group, substituted or unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, substituted or unsubstituted aryl group having 6 to 20 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted carbon number 1 to 20 alkoxy groups, substituted or unsubstituted amino groups having 0 to 20 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted acyl groups having 1 to 20 carbon atoms, substituted or unsubstituted 2 to 20 carbon atoms An alkoxycarbonyl group, a substituted or unsubstituted alkylloyloxy group having 1 to 20 carbon atoms, a substituted or unsubstituted arylloyloxy group having 7 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 20 carbon atoms, or a divalent group of these groups A group (one or more groups selected from the group consisting of substituted or unsubstituted alkylene groups, substituted or unsubstituted arylene groups, and ether groups);

R 'and X are each independently a hydrogen atom, a hydroxyl group, a cyano group, a nitro group, a substituted or unsubstituted heterocyclic group, a halogen atom, or a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, substituted or unsubstituted Branched aliphatic hydrocarbon group having 3 to 20 carbon atoms, substituted or unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, substituted or unsubstituted aryl group having 6 to 20 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, substitution Or an unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted amino group having 0 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted acyl group having 1 to 20 carbon atoms, a substituted or unsubstituted group, An alkoxycarbonyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkylloyloxy group having 1 to 20 carbon atoms, a substituted or unsubstituted arylloyloxy group having 7 to 20 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 20 carbon atoms, or A group in which these groups and a divalent group (one or more groups selected from the group consisting of substituted or unsubstituted alkylene groups, substituted or unsubstituted arylene groups, and ether groups) are bonded,

Also, in the plane of the 16-membered ring, the directions of the other three R 'relative to the direction of one R' are the directions of the cis-cis-trans in clockwise order.)

2. In the formula (1), the resist composition according to item 1, wherein X is a hydrogen atom, a hydroxyl group, or a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms.

3. In the said Formula (1), R 'is the group represented by following formula (2), and X is a hydrogen atom, The resist composition as described in 1 paragraph.

[Formula 2]

(In formula (2), p is an integer from 0 to 4,

R ¹² is each independently a cyano group, a nitro group, a halogen atom, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 14 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 14 carbon atoms, substituted or unsubstituted, A cyclic aliphatic hydrocarbon group having 3 to 14 carbon atoms, or a group represented by the following formula (3),

[Formula 3]

In the formula (3), R ⁴ is each independently a cyano group, a nitro group, a substituted or unsubstituted heterocyclic group, a halogen atom, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 14 carbon atoms, a substituted or unsubstituted carbon number. 3 to 14 branched aliphatic hydrocarbon groups, substituted or unsubstituted cyclic aliphatic hydrocarbon groups having 3 to 14 carbon atoms, substituted or unsubstituted aryl groups having 6 to 14 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 14 carbon atoms, or substituted or It is an unsubstituted alkylsilyl group having 1 to 14 carbon atoms, and q is an integer from 0 to 5.)

4. In the said Formula (1), R 'is the group represented by following formula (4), and R and X are hydrogen atoms, The resist composition of Claim 1.

[Formula 4]

5. The resist composition according to any one of items 1 to 4, wherein the content of the solvent is 20 to 99 mass%, and the content of components other than the solvent is 1 to 80 mass%.

6. An acid generator that directly or indirectly generates acid by irradiation of any one radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet (EUV), X-ray, and ion beam ( The resist composition according to any one of claims 1 to 5, further comprising C).

7. The resist composition according to any one of items 1 to 6, further comprising an acid crosslinking agent (G).

8. The resist composition according to any one of items 1 to 7, further comprising an acid diffusion control agent (E).

9. Components other than the solvent include the resist substrate (A), an acid generator (C), an acid crosslinking agent (G), and an acid diffusion control agent (E),

The content of the resist base material (A) is 50.000 to 99.498 parts by mass, the content of the acid generator (C) is 0.001 to 49.000 parts by mass, and the acid crosslinking agent (G) relative to 100 parts by mass of the total content of the components other than the solvent The resist composition according to any one of claims 1 to 8, wherein the content is 0.500 to 49.000 parts by mass, and the content of the acid diffusion control agent (E) is 0.001 to 49.000 parts by mass.

10. The resist composition according to any one of items 1 to 9, wherein an amorphous film can be formed by spin coating.

11. The resist composition according to item 10, wherein a dissolution rate of the amorphous film in a developer at 23 ° C. is 10 Pa / sec or more.

12. The resist according to claim 10, wherein the dissolution rate of the amorphous film after irradiation with KrF excimer laser, extreme ultraviolet, electron beam or X-rays, or the amorphous film after heating at 20 to 250 ° C, in a developer is 5 kPa / sec or less. Composition.

13. The step of applying the resist composition according to any one of items 1 to 12 onto a substrate and forming a resist film,

A step of exposing the resist film,

Process for developing the exposed resist film,

Method of manufacturing a resist pattern comprising a.

14. Compound represented by the following formula (1).

[Formula 5]

(In formula (1), R is each independently a hydrogen atom, a substituted or unsubstituted heterocyclic group, a halogen atom, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted 3 to 20 carbon atoms. Branched aliphatic hydrocarbon group, substituted or unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, substituted or unsubstituted aryl group having 6 to 20 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted carbon number 1 to 20 alkoxy groups, substituted or unsubstituted amino groups having 0 to 20 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted acyl groups having 1 to 20 carbon atoms, substituted or unsubstituted 2 to 20 carbon atoms An alkoxycarbonyl group, a substituted or unsubstituted alkylloyloxy group having 1 to 20 carbon atoms, a substituted or unsubstituted arylloyloxy group having 7 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 20 carbon atoms, or a divalent group of these groups A group (one or more groups selected from the group consisting of substituted or unsubstituted alkylene groups, substituted or unsubstituted arylene groups, and ether groups);

R 'and X are each independently a hydrogen atom, a hydroxyl group, a cyano group, a nitro group, a substituted or unsubstituted heterocyclic group, a halogen atom, or a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, substituted or unsubstituted Branched aliphatic hydrocarbon group having 3 to 20 carbon atoms, substituted or unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, substituted or unsubstituted aryl group having 6 to 20 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, substitution Or an unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted amino group having 0 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted acyl group having 1 to 20 carbon atoms, a substituted or unsubstituted group, An alkoxycarbonyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkylloyloxy group having 1 to 20 carbon atoms, a substituted or unsubstituted arylloyloxy group having 7 to 20 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 20 carbon atoms, or A group in which these groups and a divalent group (one or more groups selected from the group consisting of substituted or unsubstituted alkylene groups, substituted or unsubstituted arylene groups, and ether groups) are bonded,

Also, in the plane of the 16-membered ring, the directions of the other three R 'relative to the direction of one R' are the directions of the cis-cis-trans in clockwise order.)

15. The compound according to Item 14, wherein X is a hydrogen atom, a hydroxyl group, or a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms.

16. The compound according to Item 14, wherein R 'is a group represented by the following Formula (2), and X is a hydrogen atom.

[Formula 6]

(In formula (2), p is an integer from 0 to 4,

R ¹² is each independently a cyano group, a nitro group, a halogen atom, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 14 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 14 carbon atoms, substituted or unsubstituted, A cyclic aliphatic hydrocarbon group having 3 to 14 carbon atoms, or a group represented by the following formula (3),

[Formula 7]

In the formula (3), R ⁴ is each independently a cyano group, a nitro group, a substituted or unsubstituted heterocyclic group, a halogen atom, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 14 carbon atoms, a substituted or unsubstituted carbon number. 3 to 14 branched aliphatic hydrocarbon groups, substituted or unsubstituted cyclic aliphatic hydrocarbon groups having 3 to 14 carbon atoms, substituted or unsubstituted aryl groups having 6 to 14 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 14 carbon atoms, or substituted or It is an unsubstituted alkylsilyl group having 1 to 14 carbon atoms, and q is an integer from 0 to 5.)

17. The compound according to item 14, wherein R 'is a group represented by the following formula (4) in the formula (1), and R and X are hydrogen atoms.

[Formula 8]

According to the present invention, there is provided a specific stereoisomer having high solubility in a safety solvent, a high sensitivity, a small roughness, and a resist composition giving a resist pattern of a good shape, and a method of manufacturing a resist pattern using the composition Can be.

Hereinafter, embodiments of the present invention (hereinafter also referred to as "this embodiment") will be described in detail. In addition, the following embodiment is an illustration for demonstrating this invention, and this invention is not limited only to that embodiment.

[Compound represented by formula (1)]

The compound of this embodiment is a compound represented by the following formula (1).

[Formula 9]

(In formula (1), R is each independently a hydrogen atom, a substituted or unsubstituted heterocyclic group, a halogen atom, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted 3 to 20 carbon atoms. Branched aliphatic hydrocarbon group, substituted or unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, substituted or unsubstituted aryl group having 6 to 20 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted carbon number 1 to 20 alkoxy groups, substituted or unsubstituted amino groups having 0 to 20 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted acyl groups having 1 to 20 carbon atoms, substituted or unsubstituted 2 to 20 carbon atoms An alkoxycarbonyl group, a substituted or unsubstituted alkylloyloxy group having 1 to 20 carbon atoms, a substituted or unsubstituted arylloyloxy group having 7 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 20 carbon atoms, or a divalent group of these groups A group (one or more groups selected from the group consisting of substituted or unsubstituted alkylene groups, substituted or unsubstituted arylene groups, and ether groups);

R 'and X are each independently a hydrogen atom, a hydroxyl group, a cyano group, a nitro group, a substituted or unsubstituted heterocyclic group, a halogen atom, or a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, substituted or unsubstituted Branched aliphatic hydrocarbon group having 3 to 20 carbon atoms, substituted or unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, substituted or unsubstituted aryl group having 6 to 20 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, substitution Or an unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted amino group having 0 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted acyl group having 1 to 20 carbon atoms, a substituted or unsubstituted group, An alkoxycarbonyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkylloyloxy group having 1 to 20 carbon atoms, a substituted or unsubstituted arylloyloxy group having 7 to 20 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 20 carbon atoms, or A group in which these groups and a divalent group (one or more groups selected from the group consisting of substituted or unsubstituted alkylene groups, substituted or unsubstituted arylene groups, and ether groups) are bonded,

Also, in the plane of the 16-membered ring, the directions of the other three R 'relative to the direction of one R' are the directions of the cis-cis-trans in clockwise order.)

As described above, in the compound represented by the formula (1), in the plane of the 16-membered ring, the directions of the other three R's relative to the direction of any one R 'are cis-cis-trans in clockwise order. Is a specific stereoisomer (hereinafter also referred to as "cct body"). In this embodiment, in the resist composition described later, a component containing such a specific stereoisomer (the compound represented by the formula (1)) is used as a resist substrate. Since the specific stereoisomer (the compound represented by the formula (1)) has high solubility in a safety solvent, the resist composition using a resist substrate containing the compound represented by the formula (1) as a main component has high sensitivity. It is possible to stably give a resist pattern having a small roughness and good shape.

The compound represented by the formula (1) is a specific stereoisomer of the four stereoisomers that the calix compound represented by the following formula (Z) can constitute.

[Formula 10]

(In formula (Z), R, R 'and X are the same as R, R' and X in the formula (1).)

The compound represented by the formula (Z) is a 16-membered ring oligomer in which a benzene ring having two ROs is wound with a methyl group or a methylene group as the parawi of the two ROs. Accordingly, with respect to the plane of the 16-membered ring, since four R's each have an upward and downward coupling, cis-trans isomers (stereoisomers) are present in each. Accordingly, in the compound represented by the formula (Z), four stereoisomers exist as stereoisomers that the compounds having the same formula can constitute. That is, these four stereoisomers are (ccc), (ctt), (cct), and (tct), as shown below.

In the formula (Z), in the (ccc) body, in the plane of the 16-membered ring, the directions of the other three R 'relative to the direction of any one R' become the direction of the cis-cis-cis in clockwise order. It is a compound that takes a three-dimensional structure.

In the formula (Z), in the (ctt) body, in the plane of the 16-membered ring, the directions of the other three R 'relative to the direction of any one R' become the direction of the cis-trans-trans in clockwise order. It is a compound that takes a three-dimensional structure.

The (cct) body, in the formula (Z), in the plane of the 16-membered ring, the directions of the other three R 'relative to the direction of any one R' become the direction of the cis-cis-trans in clockwise order. It is a compound that takes a three-dimensional structure (hereinafter sometimes referred to as "(cct) body").

The (tct) body, in the formula (Z), in the plane of the 16-membered ring, the directions of the other three R 'relative to the direction of any one R' become the direction of trans-cis-trans in clockwise order. It is a compound that takes a three-dimensional structure.

In addition, from the viewpoint of high heat resistance and high sensitivity of the resist composition, in the formula (1), X is preferably a hydrogen atom, a hydroxyl group, or a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms. In particular, in the formula (1), R 'is more preferably a group represented by the following formula (2), and X is more preferably a hydrogen atom.

[Formula 11]

(In formula (2), p is an integer from 0 to 4,

R ¹² is each independently a cyano group, a nitro group, a halogen atom, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 14 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 14 carbon atoms, substituted or unsubstituted, A cyclic aliphatic hydrocarbon group having 3 to 14 carbon atoms, or a group represented by the following formula (3),

[Formula 12]

In the formula (3), R ⁴ is each independently a cyano group, a nitro group, a substituted or unsubstituted heterocyclic group, a halogen atom, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 14 carbon atoms, a substituted or unsubstituted carbon number. 3 to 14 branched aliphatic hydrocarbon groups, substituted or unsubstituted cyclic aliphatic hydrocarbon groups having 3 to 14 carbon atoms, substituted or unsubstituted aryl groups having 6 to 14 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 14 carbon atoms, or substituted or It is an unsubstituted alkylsilyl group having 1 to 14 carbon atoms, and q is an integer from 0 to 5.)

That is, it is preferable that the compound of this embodiment is a specific stereoisomer ((cct) form) represented by the following formula (1-1). The resist composition obtained by using the resist base material which has such a specific stereoisomer as a main component tends to improve heat resistance and sensitivity.

[Formula 13]

(In formula (1-1), R and R ¹² are synonymous with R and R ¹² mentioned above.)

Further, from the viewpoint of high heat resistance and high sensitivity of the resist composition, in the formula (1), R 'is more preferably a group represented by the following formula (4), and R and X are more preferably hydrogen atoms. .

[Formula 14]

That is, it is preferable that the compound of this embodiment is a specific stereoisomer ((cct) form) represented by following formula (1-2). The resist composition obtained by using the resist base material which has such a specific stereoisomer as a main component tends to further improve heat resistance and sensitivity.

[Formula 15]

In addition, the term "substitution" in the present specification, unless otherwise defined, at least one hydrogen atom of a functional group, a halogen atom, a hydroxyl group, a cyano group, a nitro group, a heterocyclic group, a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, Branched aliphatic hydrocarbon group having 3 to 20 carbon atoms, cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, aralkyl group having 7 to 30 carbon atoms, alkoxy group having 1 to 20 carbon atoms, 0 to 20 carbon atoms Amino group, alkenyl group having 2 to 20 carbon atoms, acyl group having 1 to 20 carbon atoms, alkoxycarbonyl group having 2 to 20 carbon atoms, alkyloyloxy group having 1 to 20 carbon atoms, aryloyloxy group having 7 to 30 carbon atoms, or 1 to 20 carbon atoms It means that it is substituted with the alkylsilyl group.

The unsubstituted heterocyclic group is not particularly limited, for example, a pyridyl group, bipyridyl group, pyrrolidyl group, pyrazoleyl group, imidazolyl group, isooxazolyl group, isothiazolyl group, piperidyl group, blood And a ferrazyl group, a morpholinyl group, a thiomorpholyl group, a triazole group, and a tetrazol group.

The substituted heterocyclic group is not particularly limited, but, for example, N-methylpyridyl group, N-fluoropyridyl group, N-hydroxypyridyl group, N-cyanopyridyl group, methylbipyridyl group, methylpyrrolid Dill group, methylpyrazolyl group, methylimidazolyl group, methylisooxazolyl group, methylisothiazolyl group, methylpiperidyl group, methylpiperazyl group, methylmorpholinyl group, methylthiomorpholyl group, methyltriazole group and methyltetra Sleepiness and the like.

The unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms is not particularly limited, but is, for example, a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group or hexadecyl group. And octadecyl groups.

The substituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms is not particularly limited, and examples thereof include a fluoromethyl group, a 2-hydroxyethyl group, a 3-cyanopropyl group, and a 20-nitrooctadecyl group. .

The unsubstituted branched aliphatic hydrocarbon group having 3 to 20 carbon atoms is not particularly limited, but, for example, isopropyl group, isobutyl group, tertiary butyl group, neopentyl group, 2-hexyl group, 2-octyl group, 2- And a decyl group, 2-dodecyl group, 2-hexadecyl group, and 2-octadecyl group.

The substituted C3-C20 branched aliphatic hydrocarbon group is not particularly limited, and examples thereof include 1-fluoroisopropyl group and 1-hydroxy-2-octadecyl group.

The unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms is not particularly limited, but, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclodecyl group, cyclododecyl group, cyclo And hexadecyl groups and cyclooctadecyl groups.

The substituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms is not particularly limited, and examples thereof include a 2-fluorocyclopropyl group and a 4-cyanocyclohexyl group.

The unsubstituted aryl group having 6 to 20 carbon atoms is not particularly limited, and examples thereof include a phenyl group and a naphthyl group.

The substituted aryl group having 6 to 20 carbon atoms is not particularly limited, and examples thereof include 4-isopropylphenyl group, 4-cyclohexylphenyl group, 4-methylphenyl group, and 6-fluoronaphthyl group.

The unsubstituted aralkyl group having 7 to 30 carbon atoms is not particularly limited, and examples thereof include 4-methylphenyl group, 4-ethylphenyl group, 6-methylnaphthyl group, and 2,6-dimethylnaphthyl group.

The substituted aralkyl group having 7 to 30 carbon atoms is not particularly limited, and examples thereof include a 4-fluoro-3-methylphenyl group and the like.

The unsubstituted alkoxy group having 1 to 20 carbon atoms is not particularly limited, but, for example, methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, octyloxy group, decyloxy group, dodecyloxy Period, hexadecyloxy group, octadecyloxy group, and the like.

Although a substituted C1-C20 alkoxy group is not specifically limited, For example, a chloromethoxy group, a bromoethoxy group, etc. are mentioned.

The unsubstituted amino group having 0 to 20 carbon atoms is not particularly limited, and examples thereof include an amino group, a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, a dipropylamino group, and a dibutylamino group.

The substituted amino group having 0 to 20 carbon atoms is not particularly limited, and examples thereof include a chloromethylamino group, a dibromomethylamino group, and the like.

The unsubstituted alkenyl group having 2 to 20 carbon atoms is not particularly limited, but, for example, vinyl group, propynyl group, butynyl group, pentynyl group, hexynyl group, octinyl group, decynyl group, dodecynyl group, hexadecynyl group, octa And a desinyl group.

The substituted alkenyl group having 2 to 20 carbon atoms is not particularly limited, and examples thereof include a chloropropynyl group and the like.

Unsubstituted acyl group having 1 to 20 carbon atoms, although not particularly limited, for example, formyl group, acetyl group, propanoyl group, butanoyl group, pentanoyl group, hexanoyl group, octanoyl group, decanoyl group, dodecanoyl group, hexa Decanoyl group, benzoyl group, etc. are mentioned.

Although a substituted C1-C20 acyl group is not specifically limited, For example, a chloroacetyl group etc. are mentioned.

The unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms is not particularly limited, but, for example, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, octyloxycarbonyl group, decyloxy And a carbonyl group, dodecyloxycarbonyl group, and hexadecyloxycarbonyl group.

Although a substituted C2-C20 alkoxycarbonyl group is not specifically limited, For example, a chloromethoxycarbonyl group etc. are mentioned.

The unsubstituted alkylloyloxy group having 1 to 20 carbon atoms is not particularly limited, but, for example, methoxycarbonyloxy group, ethoxycarbonyloxy group, propoxycarbonyloxy group, butoxycarbonyloxy group, And pentyloxycarbonyloxy group, hexyloxycarbonyloxy group, octyloxycarbonyloxy group, decyloxycarbonyloxy group, dodecyloxycarbonyloxy group, and hexadecyloxycarbonyloxy group.

The substituted alkyloyloxy group having 1 to 20 carbon atoms is not particularly limited, and examples thereof include a chloromethoxycarbonyloxy group and the like.

The unsubstituted aryloyloxy group having 7 to 30 carbon atoms is not particularly limited, and examples thereof include a benzoyloxy group and a naphthylcarbonyloxy group.

The substituted aryloyloxy group having 7 to 30 carbon atoms is not particularly limited, and examples thereof include chlorobenzoyloxy group and the like.

The unsubstituted alkylsilyl group having 1 to 20 carbon atoms is not particularly limited, for example, methylsilyl group, ethylsilyl group, propylsilyl group, butylsilyl group, pentylsilyl group, hexylsilyl group, octylsilyl group, decylsilyl Group, dodecylsilyl group, hexadecylsilyl group, octadecylsilyl group, and the like.

The substituted alkylsilyl group having 1 to 20 carbon atoms is not particularly limited, and examples thereof include a chloromethylsilyl group and the like.

The molecular weight of the compound (cct body) represented by the formula (1) is preferably 500 to 5000, more preferably 800 to 2000, further preferably 1000 to 2000. When the molecular weight is within the above range, the resist composition containing a resist base material containing this cct body as a main component improves the resolution while maintaining the film-forming properties required for the resist.

The glass transition temperature of the compound (cct body) represented by the formula (1) is preferably 100 ° C or higher, more preferably 120 ° C or higher, still more preferably 140 ° C or higher, particularly preferably 150 ° C or higher. . Although the upper limit of this glass transition temperature is not specifically limited, For example, it is 300 degreeC. When the glass transition temperature is within the above range, the resist composition containing a resist substrate containing this cct body as a main component has a heat resistance capable of maintaining a pattern shape in a semiconductor lithography process, and improves performance such as high resolution. do.

It is preferable that the crystallization calorific value obtained by differential scanning calorimetry of the glass transition temperature of the compound (cct body) represented by the formula (1) is less than 20 J / g. In addition, in the compound (cct body) represented by the formula (1), (crystallization temperature)-(glass transition temperature) is preferably 70 ° C or higher, more preferably 80 ° C or higher, even more preferably 100 ℃ or higher, particularly preferably 130 ° C or higher. The upper limit of this (crystallization temperature)-(glass transition temperature) is not particularly limited, but is, for example, 200 ° C. In the compound (cct body) represented by the formula (1), if the calorific value of crystallization is less than 20 J / g, or if the (crystallization temperature)-(glass transition temperature) is within the above range, a resist substrate containing this cct body as a main component The resist composition containing the film is easy to form an amorphous film by spin coating, and the film-forming properties required for the resist are maintained over a long period of time, and the resolution is further improved.

In this embodiment, the crystallization calorific value, crystallization temperature, and glass transition temperature can be obtained as follows by differential scanning calorimetry (DSC) using DSC / TA-50WS manufactured by Shimadzu Corporation. About 10mg of the sample is put in a sealed container made of aluminum, and heated to a melting point or higher at a heating rate of 20 ° C / min in a nitrogen gas stream (50mL / min). After the rapid cooling, the sample is again heated to a melting point or higher at a heating rate of 20 ° C / min in a nitrogen gas stream (30 mL / min). In addition, after rapid cooling, the sample is heated up to 400 ° C. again in a nitrogen gas stream (30 mL / min) at a heating rate of 20 ° C./min. In the obtained DSC curve, the temperature of the midpoint (where the specific heat is changed in half) of the step difference of the baseline changed in step shape is the glass transition temperature (Tg), and the temperature of the exothermic peak appearing after that is called the crystallization temperature. In addition, the calorific value is determined by calculating the calorific value from the area of the region surrounded by the heating peak and the baseline.

The compound (cct body) represented by the formula (1) is under normal pressure at 100 ° C, preferably 120 ° C, more preferably 130 ° C, more preferably 140 ° C, particularly preferably 150 ° C, It is preferable that the sublimation property is low. The low sublimation property means that in thermogravimetric analysis, the weight loss when maintained at a predetermined temperature for 10 minutes is 10% or less, preferably 5% or less, more preferably 3% or less, and even more preferably 1%. Hereinafter, it means that it is 0.1% or less particularly preferably. The compound (cct body) represented by the formula (1) has a low sublimation property, thereby preventing contamination of the exposure apparatus due to outgas during exposure. In addition, the resist composition containing a resist base material having such a cct body as a main component has low line edge roughness (LER), so that a good pattern shape can be obtained.

The compound (cct body) represented by the formula (1) preferably satisfies F <3.0 (F represents the total number of atoms / (total number of carbon atoms-total number of oxygen atoms)), and more preferably F <2.5 is satisfied, and more preferably F <2.0 is satisfied. Although the lower limit of this F is not particularly limited, it is, for example, 1.5. Since this F satisfies the above conditions, the resist composition containing a resist substrate containing this cct body as a main component is excellent in dry etching resistance.

The compound (cct body) represented by the formula (1) has high solubility in a safety solvent. The safety solvent is not particularly limited, for example, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), cyclopentanone (CPN), 2-heptan And at least one solvent selected from the group consisting of warm, anisole, butyl acetate, ethyl propionate and ethyl lactate.

The compound (cct body) represented by the formula (1) is, in the above-mentioned safety solvent, in a solvent exhibiting the highest solubility with respect to this compound, at 23 ° C, preferably 1% by mass or more, more preferably 5 It dissolves in mass% or more, more preferably 10 mass% or more. In particular, the compound (cct body) represented by the formula (1) is, among solvents selected from the group consisting of PGMEA, PGME, and CHN, at a solvent exhibiting the highest solubility for this compound, preferably at 23 ° C. Dissolves 20% by mass or more. Furthermore, the compound (cct body) represented by the formula (1) is particularly preferably dissolved in PGMEA at 23 ° C at 20% by mass or more. When the compound (cct body) represented by the formula (1) has the above-mentioned solubility, the resist composition containing a resist substrate containing the cct body as a main component can be used in a semiconductor manufacturing process in actual production. .

To the extent that the effect of the present invention is not inhibited, the compound represented by the formula (1) (cct body) is visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet (EUV), X-ray and ion beam irradiation or A crosslinking reactive group that causes a crosslinking reaction may be introduced by an organic chemical reaction. The method for introducing the crosslinking reactive group to the compound (cct body) represented by the formula (1) is not particularly limited, and for example, a method of reacting the compound and the crosslinking reactive group introduction initiator under a base catalyst is mentioned. have. Although it does not specifically limit as a crosslinking reactive group, For example, a carbon-carbon multiple bond, an epoxy group, an azide group, a halogenated phenyl group, and a chloromethyl group are mentioned. The initiator for introducing the crosslinking reactive group is not particularly limited, and examples thereof include carboxylic acid derivatives such as acids, acid chlorides, acid anhydrides, and dicarbonates having such crosslinking reactive groups, alkyl halides, and the like. A resist composition comprising a compound having a crosslinking reactive group is also useful as a high-resolution, high-heat-resistance, and solvent-soluble, non-polymer-based resist composition.

A non-dissociable, functional group may be introduced into at least one phenolic hydroxyl group of the compound (cct form) represented by the formula (1) within a range that does not impair the effects of the present invention. The non-dissociable functional group refers to a characteristic group that does not cleave under an acid catalyst and does not generate an alkali-soluble group. The non-dissociable functional group is not particularly limited, but, for example, a C1-20 alkyl group, a C3-20 cycloalkyl group, a C6-20 aryl group, and a C1-20 alkoxy group that do not decompose under the action of an acid. And functional groups selected from the group consisting of a practical group, a cyano group, a nitro group, a hydroxyl group, a heterocyclic group, a halogen, a carboxyl group, a C1-20 alkylsilane, and derivatives thereof.

A naphthoquinone diazide ester group may be introduced into the phenolic hydroxyl group of the compound (cct form) represented by the formula (1) within a range that does not impair the effects of the present invention. A compound in which a naphthoquinone diazide ester group is introduced into at least one phenolic hydroxyl group of this compound can be used as a main component of a negative-type resist composition, and used as a main component of a positive-type resist composition, or as an acid generator or additive. It can be added to a resist composition.

To the extent that the effects of the present invention are not inhibited, an acid-generating functional group that generates an acid upon irradiation with radiation may be introduced into at least one phenolic hydroxyl group of the compound (cct form) represented by the formula (1). . A compound in which an acid-generating functional group is introduced into at least one phenolic hydroxyl group of this compound can be used as a main component of a negative resist composition and can be added to the resist composition as an additive.

It is preferable that the compound (cct body) represented by the formula (1) can form an amorphous film by spin coating. In addition, it can be applied to general semiconductor manufacturing processes.

The compound (cct body) represented by the formula (1) is useful as a negative resist substrate that becomes a poorly soluble compound in a developer by irradiating KrF excimer laser, extreme ultraviolet, electron beam, or X-ray. It is thought that the condensation reaction between these compounds is induced by irradiating KrF excimer laser, extreme ultraviolet, electron beam or X-ray to this compound, and it is considered to be a poorly soluble compound in the alkali developer. In the resist pattern thus obtained, the LER is very small.

[Method for preparing compound represented by formula (1)]

The compound (cct body) represented by the formula (1) is not particularly limited, but is, for example, one or more compounds selected from the group consisting of aldehyde compounds (A1) and phenolic compounds (A2). Obtained by condensation reaction of one or more compounds selected from the group.

Preferably, the aldehyde compound (A1) is a compound having 2 to 59 carbon atoms having a monovalent group containing 1 to 4 formyl groups, and the phenolic compound (A2) is 1 to 3 phenolic hydroxyl groups It is a compound having 6 to 15 carbon atoms.

The aldehyde compound (A1) has 2 to 59 carbon atoms, has a monovalent group containing 1 to 4 formyl groups, and is selected from aromatic aldehyde compounds (A1A) and aliphatic aldehyde compounds (A1B). The aromatic aldehyde compound (A1A) is preferably a benzaldehyde compound having 7 to 24 carbon atoms. Although it does not specifically limit as a benzaldehyde compound of 7-24 carbon atoms, For example, the benzaldehyde of 7-24 carbon atoms which has a substituent containing at least 1 alicyclic or aromatic ring other than an aromatic ring of benzaldehyde is mentioned. Specific examples of the benzaldehyde are not particularly limited, for example, methyl benzaldehyde, ethyl benzaldehyde, propyl benzaldehyde, butyl benzaldehyde, cyclopropyl benzaldehyde, cyclobutane benzaldehyde, cyclopentane benzaldehyde, cyclohexane benzaldehyde, phenylbenzaldehyde, naphthylaldehyde, And benzaldehyde, adamantyl benzaldehyde, norbornyl benzaldehyde, and lactyl benzaldehyde. Especially, propyl benzaldehyde, cyclohexyl benzaldehyde, and phenyl benzaldehyde are preferable, and propyl benzaldehyde and cyclohexyl benzaldehyde are more preferable. The aromatic aldehyde compound (A1A) may have a straight-chain or branched alkyl group having 1 to 4 carbon atoms, a cyano group, a hydroxyl group, a halogen, and the like within a range that does not impair the effects of the present invention. The aromatic aldehyde compound (A1A) may be used alone or in combination of two or more. The aliphatic aldehyde compound (A1B) may have a cyano group, a hydroxyl group, a halogen, and the like within a range that does not impair the effects of the present invention. The aliphatic aldehyde compound (A1B) may be used alone or in combination of two or more.

The phenolic compound (A2) preferably has 6 to 15 carbon atoms. Moreover, it is preferable that a phenolic compound (A2) has 1-3 phenolic hydroxyl groups. Although it does not specifically limit as a specific example of a phenolic compound (A2), For example, For example, phenol, catechol, resorcinol, hydroquinone, pyrogallol, 3-methoxyphenol, 3-ethoxyphenol, 3- And cyclohexyloxyphenol, 1,3-dimethoxybenzene, 1,3-diethoxybenzene, and 1,3-dicyclohexyloxybenzene. Among them, resorcinol, pyrogallol, 3-methoxyphenol, 3-ethoxyphenol, 3-cyclohexyloxyphenol, 1,3-dimethoxybenzene, 1,3-diethoxybenzene, 1,3-dicy Clohexyloxybenzene is preferred, and resorcinol is more preferred. The phenolic compound (A2) may have a straight-chain or branched alkyl group having 1 to 4 carbon atoms, a cyano group, a hydroxyl group, a halogen, or the like in a range that does not impair the effects of the present invention. The phenolic compounds (A2) may be used alone or in combination of two or more.

Although it does not specifically limit about the specific manufacturing method of the compound represented by said Formula (1), For example, the following method is mentioned. First, in an organic solvent such as methanol or ethanol, 0.1 to 10 mol of the phenolic compound (A2) is added to 1 mol of the aldehyde compound (A1) under the catalyst of an acid catalyst (hydrochloric acid, sulfuric acid, or paratoluenesulfonic acid). The reaction is performed at 20 to 150 ° C for 0.5 to 20 hours. Subsequently, the obtained reaction product is washed with alcohols such as filtration and methanol, washed with water, separated by filtration, and dried, whereby the compound represented by the formula (1) can be obtained. Instead of an acid catalyst, a basic catalyst (sodium hydroxide, barium hydroxide or 1,8-diazabicyclo [5.4.0] undecene-7, etc.) is used, and similar reaction also yields the compound represented by the formula (1). Can be. In addition, the compound represented by the formula (1) may be prepared by making the aldehyde compound (A1) a dihalide with hydrogen halide or a halogen gas, and reacting the isolated dihalide with a phenolic compound (A2). have.

The method of isolating the specific stereoisomer (cct body) used in the present embodiment from the reaction product obtained by the above reaction, or the method of obtaining a resist substrate containing this stereoisomer as a main component is a recrystallization method, column chromatography, or fractionation. A known method such as separation by liquid chromatography can be employed. In addition, a method by optimizing reaction solvent and reaction temperature and time at the time of manufacture can also be employed. Two or more of these methods may be combined.

The compound (cct body) represented by the formula (1) can be purified as necessary for the purpose of reducing the amount of remaining metal and improving the purity. In addition, when an acid catalyst and a co-catalyst remain in the compound (cct body) represented by the formula (1), generally, the resist composition containing a resist substrate containing the cct body as a main component deteriorates storage stability. , When a basic catalyst remains in the compound (cct body) represented by the formula (1), in general, the resist composition containing a resist substrate containing the cct body as a main component has a reduced sensitivity. Therefore, purification for the purpose of reducing these residual catalysts can also be carried out.

The acidic aqueous solution, basic aqueous solution, ion-exchange resin and silica gel column chromatography used for this purification are appropriately selected depending on the amount or type of metal, acidic compound and basic compound to be removed, and the type of compound desired. It is possible. Although it is not specifically limited as an acidic aqueous solution, For example, hydrochloric acid, nitric acid, and acetic acid aqueous solution whose concentration is 0.01-10 mol / L are mentioned. Although it does not specifically limit as a basic aqueous solution, For example, the aqueous ammonia solution whose concentration is 0.01-10 mol / L is mentioned. Although it does not specifically limit as an ion exchange resin, For example, cation exchange resin is mentioned. Although it is not specifically limited as a commercial item of cation exchange resin, For example, Amberlyst 15J-HG Dry by Organo Corporation etc. are mentioned.

It can also be dried after the purification. Drying can be performed by a known method, and is not particularly limited, but, for example, vacuum drying under the condition that the compound represented by the formula (1) (and the resist substrate containing the compound as a main component) is not denatured. Hot air drying, blowing air drying, and the like.

It is preferable that the compound (cct body) represented by the formula (1) can form an amorphous film by spin coating. In addition, it can be applied to general semiconductor manufacturing processes.

The compound (cct body) represented by the formula (1) is useful as a negative resist base material that becomes a poorly soluble compound in a developer by irradiating KrF excimer laser, extreme ultraviolet, electron beam, or X-ray. It is thought that the condensation reaction between the compounds is induced by irradiating KrF excimer laser, extreme ultraviolet rays, electron beams or X-rays to this compound, and the compound becomes poorly soluble in the alkali developer. In the resist pattern thus obtained, the LER is very small.

The compound (cct body) represented by the formula (1) can be used as a main component of a negative-type resist base material, and can be added to the resist composition as an additive for improving sensitivity or improving etch resistance, for example. have. In this case, the addition amount of the compound (cct body) represented by the formula (1) is preferably 1 to 49.999 mass% of the total weight of the solid component of the resist composition.

[Resist composition]

The resist composition of the present embodiment is a composition comprising a resist substrate and a solvent, wherein the resist substrate contains a compound represented by the formula (1) and is represented by the formula (1) occupied by the resist substrate. The proportion of the compound is 50 to 100% by mass.

In the resist composition of the present embodiment, the content of the solvent is preferably 20 to 99 mass%, more preferably 50 to 99 mass%, even more preferably 60 to 98 mass%, and 90 to 98 mass% % Is particularly preferred. In addition, in the resist composition of the present embodiment, the content of components other than the solvent is preferably 1 to 80% by mass, more preferably 1 to 50% by mass, and even more preferably 2 to 40% by mass. And 2 to 10% by mass is particularly preferable. By setting the range of the content of the solvent and the components other than the solvent to this range, the resist composition is easy to prepare a solution by dissolving and dissolving the resist substrate, and can also realize film thickness control and mixing with various compounds. have.

(Resist base)

In the resist composition of the present embodiment, the proportion of the compound represented by the formula (1) in the resist substrate is in the range of 50 to 100% by mass. By setting the ratio of the compound represented by the formula (1) to the resist substrate within this range, the resist composition has high sensitivity, low roughness, and a resist pattern of a better shape can be stably obtained. The proportion of the compound represented by the formula (1) in the resist substrate is preferably in the range of 55 to 100% by mass, more preferably in the range of 60 to 100% by mass.

In addition, as for the resist base material used for this embodiment, the compound (cct body) represented by said formula (1) should just be contained in the range of 50-100 mass%, and after isolate | separating this cct body, this cct body and Alternatively, it may be used as a resist substrate blended with other stereoisomers or other resist compounds, or the isolated cct body may be used alone as a resist substrate. Alternatively, the cct body can also be used as a resist substrate in a state containing other stereoisomers without isolation after synthesis.

In the resist composition of the present embodiment, the content of the resist substrate is the total content of components other than the solvent (for example, the resist substrate (A), and the acid generator (C) and acid crosslinking agent (G). , Acid diffusion control agent (E) and other components (F), the total content of components used arbitrarily) is preferably 50.000 to 99.9 parts by mass, more preferably 50.000 to 90.000 parts by mass, further It is preferably 50.000 to 85.000 parts by mass, particularly preferably 50.000 to 70.000 parts by mass. When the content of the resist substrate is within the above range, the resist composition has high resolution, and the line edge roughness is reduced.

(Characteristics of resist composition)

It is preferable that the resist composition of this embodiment can form an amorphous film by spin coating. The dissolution rate of the amorphous film formed by spin-coating the resist composition of this embodiment with respect to the developer at 23 ° C is preferably 10 kPa / sec or more, more preferably 10 to 10000 kPa / sec, and 100 to 1000 kPa / sec. It is more preferable. If the dissolution rate is 10 kPa / sec or more, the amorphous film can be dissolved in a developer and used as a resist. Moreover, when this dissolution rate is 10000 kPa / sec or less, resolution may be improved. This is presumed to be because the contrast between the unexposed portion soluble in the developer and the exposed portion not soluble in the developer increases due to the change in solubility before and after exposure of the compound represented by the formula (1). In addition, it has the effect of reducing LER and reducing defects.

Although the method of controlling the dissolution rate within the above range is not particularly limited, for example, by controlling the content ratio of components other than the solvent, or by using a dissolution accelerator and / or a dissolution control agent described later. And a control method.

Further, in the present embodiment, the dissolution rate can be determined by a known method, but, for example, the film thickness change before and after immersing the amorphous film in a developer can be determined by the ellipsometer method or the crystal oscillator microbalance method (QCM method). It can be obtained by measuring.

The resist composition of the present embodiment is the amorphous film (part exposed by this radiation) after irradiating radiation such as KrF excimer laser, extreme ultraviolet, electron beam or X-ray, or the amorphous film after heating at 20 to 250 ° C. The dissolution rate of the film in the developer at 23 ° C is preferably 5 kPa / sec or less, more preferably 0.05-5 kPa / sec, and even more preferably 0.0005-5 kPa / sec. If the dissolution rate is 5 Pa / sec or less, the amorphous film is insoluble in a developer and can be used as a resist. Moreover, when this dissolution rate is 0.0005 kPa / sec or more, resolution may be improved. This is presumed to be because the surface portion of the micro of the compound represented by the formula (1) is dissolved and the LER is reduced. It also has a reduction effect of defects.

Although the method of controlling the dissolution rate within the above range is not particularly limited, for example, by controlling the content ratio of components other than the solvent, or by using a dissolution accelerator and / or a dissolution control agent described later. And a control method.

(Acid Generator (C))

The resist composition of the present embodiment can directly or indirectly acid an acid by irradiation with any one type of radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet (EUV), X-ray, and ion beam. It is preferable to include one or more acid generators (C). In the resist composition of the present embodiment, the content of the acid generator (C) is preferably 0.001 to 49 parts by mass, more preferably 1 to 40 parts by mass, with respect to 100 parts by mass of the total content of components other than the above solvent, 3-30 mass parts is more preferable, and 10-25 mass parts is especially preferable. When the content of the acid generator (C) is within the above range, the resist composition has a high sensitivity and a low edge roughness pattern profile is obtained. In this embodiment, when acid is generated in the system, the method of generating the acid is not limited. If an excimer laser is used instead of ultraviolet rays such as g-rays or i-rays, finer processing is possible, and further fine processing is possible by using electron beams, extreme ultraviolet rays, X-rays, and ion beams as high-energy rays.

It is preferable that it is at least 1 sort (s) selected from the group which consists of a compound represented by following formula (7-1)-(7-8) as said acid generator (C).

[Formula 16]

(In formula (7-1), R ¹³ may be the same or different, and each independently a hydrogen atom, a straight chain, a branched or cyclic alkyl group, a straight chain, a branched or cyclic alkoxy group, and a hydroxyl group. Or a halogen atom; X ^- is a sulfonic acid ion or halide ion having an alkyl group, an aryl group, a halogen-substituted alkyl group or a halogen-substituted aryl group.)

The compound represented by the formula (7-1) is diphenyltrimethylphenylsulfonium p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoromethanesulfonate, triphenylsulfonate Phonium nonafluoro-n-butanesulfonate, diphenyltolylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, diphenyl-4-methylphenylsulfonium trifluor Romethanesulfonate, di-2,4,6-trimethylphenylsulfonium trifluoromethanesulfonate, diphenyl-4-t-butoxyphenylsulfonium trifluoromethanesulfonate, diphenyl-4-t- Butoxyphenylsulfonium nonafluoro-n-butanesulfonate, diphenyl-4-hydroxyphenylsulfonium trifluoromethanesulfonate, bis (4-fluorophenyl) -4-hydroxyphenylsulfonium trifluor Romethanesulfonate, diphenyl-4-hydroxyphenylsulfonium nonafluoro-n-butanesulfonate, bis (4-hydroxyphenyl) -phenylsulfonium trifluoromethanesulfonate, tri (4-methoxy Phenyl) sulfonium trifluoromethanesulfonate, tri (4-fluorophenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfoniumbenzenesulfonate, diphenyl-2 , 4,6-trimethylphenyl-p-toluenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-2-trifluoromethylbenzenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonate Phonium-4-trifluoromethylbenzenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-2,4-difluorobenzenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium Hexafluorobenzenesulfonate, diphenylnaphthylsulfonium trifluoromethanesulfonate, diphenyl-4-hydroxyphenylsulfonium-p-toluenesulfonate, triphenylsulfonium10-campersulfonate, diphenyl-4 It is preferable that it is at least 1 sort (s) selected from the group which consists of -hydroxyphenylsulfonium 10-camper sulfonate and cyclo (1,3-perfluoropropane disulfone) imide. Among them, the compound represented by the formula (7-1) includes diphenyltrimethylphenylsulfonium p-toluenesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, and tri Phenylsulfonium nonafluoromethanesulfonate is more preferred.

[Formula 17]

(In Formula (7-2), R ¹⁴ may be the same or different, and each independently a hydrogen atom, a straight chain, a branched or cyclic alkyl group, a straight chain, a branched or cyclic alkoxy group, a hydroxyl group. Or a halogen atom, X ^- is the same as in the formula (7-1).)

The compound represented by the formula (7-2) is bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfo Nate, bis (4-t-butylphenyl) iodonium perfluoro-n-octanesulfonate, bis (4-t-butylphenyl) iodonium p-toluenesulfonate, bis (4-t-butylphenyl) iodide Niumbenzenesulfonate, bis (4-t-butylphenyl) iodonium-2-trifluoromethylbenzenesulfonate, bis (4-t-butylphenyl) iodonium-4-trifluoromethylbenzenesulfonate, bis (4-t-butylphenyl) iodonium-2,4-difluorobenzenesulfonate, bis (4-t-butylphenyl) iodoniumhexafluorobenzenesulfonate, bis (4-t-butylphenyl) iodine Nium 10-camper sulfonate, diphenyl iodonium trifluoromethane sulfonate, diphenyl iodonium nonafluoro-n-butane sulfonate, diphenyl iodonium perfluoro-n-octane sulfonate, diphenyl iodonium p-toluene sulfonate, diphenyl iodonium benzene sulfonate, diphenyl iodonium 10- camphor sulfonate, diphenyl iodonium-2-trifluoromethylbenzenesulfonate, diphenyl iodonium-4-trifluoromethyl Benzene sulfonate, diphenyl iodonium-2,4-difluorobenzenesulfonate, diphenyl iodonium hexafluorobenzenesulfonate, di (4-trifluoromethylphenyl) iodonium trifluoromethanesulfonate, di (4-trifluoromethylphenyl) iodonium nonafluoro-n-butanesulfonate, di (4-trifluoromethylphenyl) iodonium perfluoro-n-octanesulfonate, di (4-trifluoromethylphenyl) At least one kind selected from the group consisting of iodonium p-toluenesulfonate, di (4-trifluoromethylphenyl) iodonium benzenesulfonate and di (4-trifluoromethylphenyl) iodonium 10-campersulfonate desirable.

[Formula 18]

(In formula (7-3), Q is an alkylene group, an arylene group or an alkoxy group, and R ¹⁵ is an alkyl group, an aryl group, a halogen-substituted alkyl group or a halogen-substituted aryl group.)

The compound represented by the formula (7-3) is N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethyl Sulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (trifluoromethylsulfonyl Oxy) naphthylimide, N- (10-campersulfonyloxy) succinimide, N- (10-campersulfonyloxy) phthalimide, N- (10-campersulfonyloxy) diphenylmaleimide, N- (10-campersulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (10-campersulfonyloxy) naphthylimide, N- (n -Octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (n-octanesulfonyloxy) naphthylimide, N- (p-toluenesulfonyl Oxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (p-toluenesulfonyloxy) naphthylimide, N- (2-trifluoromethylbenzenesulfonyl Oxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (2-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (4-trifluoro Methylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (4-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (purple Luobenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (perfluorobenzenesulfonyloxy) naphthylimide, N- (1-naphthalene Sulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (1-naphthalenesulfonyloxy) naphthylimide, N- (nonafluoro-n-butane Sulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (nonafluoro-n-butanesulfonyloxy) naphthylimide, N- (perfluoro -n-octanesulfonyloxy) bicyclo [2.2.1] hep-5-ene-2,3-dicarboxyimide and N- (perfluoro-n-octanesulfonyloxy) naphthylimide It is preferable that it is at least one type selected from.

[Formula 19]

(In formula (7-4), R ¹⁶ may be the same or different, and each independently, an optionally substituted straight chain, branched or cyclic alkyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, or an optionally substituted It is an aralkyl group.)

The compound represented by the formula (7-4) includes diphenyldisulfone, di (4-methylphenyl) disulfone, dinaphthyldisulfone, di (4-tert-butylphenyl) disulfone, di (4-hydroxy) Phenyl) disulfone, di (3-hydroxynaphthyl) disulfone, di (4-fluorophenyl) disulfone, di (2-fluorophenyl) disulfone and di (4-trifluoromethylphenyl) disulfone It is preferably at least one kind selected from the group consisting of.

[Formula 20]

(In formula (7-5), R ¹⁷ may be the same or different, and each independently, an optionally substituted straight chain, branched or cyclic alkyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, or an optionally substituted It is an aralkyl group.)

The compound represented by the formula (7-5) is α- (methylsulfonyloxyimino) -phenylacetonitrile, α- (methylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (trifluoro Lomethylsulfonyloxyimino) -phenylacetonitrile, α- (trifluoromethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -4-methoxyphenylacetonitrile , α- (propylsulfonyloxyimino) -4-methylphenylacetonitrile and α- (methylsulfonyloxyimino) -4-bromophenylacetonitrile.

[Formula 21]

(In formula (7-6), R ¹⁸ may be the same or different, and each independently is a halogenated alkyl group having one or more chlorine atoms and one or more bromine atoms. The number of carbon atoms in the halogenated alkyl group is 1 to 5 desirable.)

[Formula 22]

[Formula 23]

In formulas (7-7) and (7-8), R ¹⁹ and R ²⁰ are each independently an alkyl group having 1 to 3 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, cyclopentyl group, Cycloalkyl groups such as cyclohexyl groups, alkoxy groups having 1 to 3 carbon atoms such as methoxy groups, ethoxy groups and propoxy groups, or aryl groups such as phenyl groups, toluyl groups and naphthyl groups, preferably 6 to 10 carbon atoms. It is an aryl group. L ¹⁹ and L ²⁰ are each independently an organic group having a 1,2-naphthoquinone diazide group. As the organic group having 1,2-naphthoquinone diazide group, specifically, 1,2-naphthoquinone diazide-4-sulfonyl group, 1,2-naphthoquinone diazide-5-sulfonyl group, 1 1,2-quinone diazide sulfonyl groups such as, 2-naphthoquinone diazide-6-sulfonyl group are preferred. In particular, 1,2-naphthoquinone diazide-4-sulfonyl group and 1,2-naphthoquinone diazide-5-sulfonyl group are preferred. p is an integer of 1 to 3, q is an integer of 0 to 4, and 1≤p + q≤5. J ¹⁹ is a single bond, a polymethylene group having 1 to 4 carbon atoms, a cycloalkylene group, a phenylene group, a group represented by the following formula (7-7-1), a carbonyl group, an ester group, an amide group or an ether group, Y ¹⁹ is a hydrogen atom, an alkyl group or an aryl group, and X ²⁰ is a group represented by the following formula (7-8-1) independently.

[Formula 24]

[Formula 25]

(In formula (7-8-1), Z ²² is each independently an alkyl group, a cycloalkyl group, or an aryl group, R ²² is an alkyl group, a cycloalkyl group, or an alkoxyl group, and r is an integer from 0 to 3.)

Other acid generators are not particularly limited, for example, bis (p-toluenesulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (tert-butylsulfonyl) Diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, Bis (cyclohexylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, 1,3-bis (cyclohexylsulfonylazomethylsulfonyl) propane, 1, 4-bis (phenylsulfonyl azomethyl Bissulfonyl diazomethanes such as sulfonyl) butane, 1, 6-bis (phenylsulfonyl azomethyl sulfonyl) hexane, and 1, 10-bis (cyclohexyl sulfonyl azomethyl sulfonyl) decane; 2- (4-methoxyphenyl) -4,6- (bistrichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4,6- (bistrichloromethyl ) -1,3,5-triazine, tris (2,3-dibromopropyl) -1,3,5-triazine, halogen such as tris (2,3-dibromopropyl) isocyanurate And triazine derivatives.

Of the acid generators, an acid generator having an aromatic ring is preferable, and an acid generator represented by formula (7-1) or (7-2) is more preferable. An acid generator in which X ^- in formula (7-1) or (7-2) is a sulfonic acid ion having an aryl group or a halogen-substituted aryl group is more preferable, and X in formula (7-1) or (7-2) ^- a, an aryl group having sulfonic acid ion, and the acid generating agent is particularly preferred, diphenyl-trimethylphenyl sulfonium p- toluene sulfonate, triphenyl sulfonium p- toluene sulfonate, triphenyl sulfonium trifluoromethane sulfonate, Triphenylsulfonium nonafluoromethanesulfonate is particularly preferred. By using this acid generator, the resist composition can further reduce LER.

The acid generator (C) may be used alone or in combination of two or more.

(Acid crosslinking agent (G))

It is preferable that the resist composition of this embodiment contains 1 or more types of acid crosslinking agents (G). The acid crosslinking agent (G) is a compound capable of intramolecular or intermolecular crosslinking of the compound represented by the formula (1) under the catalyst of the acid generated from the acid generator (C). Although it does not specifically limit as such an acid crosslinking agent (G), For example, the compound which has 1 or more types (hereinafter also called "crosslinkable group") which can crosslink the compound represented by said formula (1) is mentioned. Can be.

Although it does not specifically limit as a specific example of such a crosslinkable group, For example, (i) hydroxy (C1-C6 alkyl group), C1-C6 alkoxy (C1-C6 alkyl group), acetoxy (C1-C6 alkyl group), etc. Hydroxyalkyl groups or groups derived therefrom; (ii) a carbonyl group such as a formyl group or a carboxy (C1-C6 alkyl group) or a group derived therefrom; (iii) nitrogen-containing group groups such as dimethylaminomethyl group, diethylaminomethyl group, dimethylolaminomethyl group, diethylolaminomethyl group, and morpholinomethyl group; (iv) glycidyl group-containing groups such as glycidyl ether group, glycidyl ester group and glycidyl amino group; (v) groups derived from aromatic groups such as C1-C6 allyloxy (C1-C6 alkyl group) and C1-C6 aralkyloxy (C1-C6 alkyl group), such as benzyloxymethyl group and benzoyloxymethyl group; (vi) polymerizable multiple bond-containing groups such as vinyl groups and isopropenyl groups. As a crosslinkable group of the acid crosslinking agent (G) used in this embodiment, a hydroxyalkyl group, an alkoxyalkyl group, etc. are preferable, and an alkoxymethyl group is particularly preferable.

The acid crosslinking agent (G) having the crosslinkable group is not particularly limited, but, for example, (i) a methylol group-containing melamine compound, a methylol group-containing benzoguanamine compound, a methylol group-containing urea compound, and a methylol group-containing glycoluril compound , Methylol group-containing compounds such as methylol group-containing phenolic compounds; (ii) alkoxyalkyl group-containing compounds such as alkoxyalkyl group-containing melamine compounds, alkoxyalkyl group-containing benzoguanamine compounds, alkoxyalkyl group-containing urea compounds, alkoxyalkyl group-containing glycoluril compounds, and alkoxyalkyl group-containing phenol compounds; (iii) carboxymethyl group-containing compounds such as carboxymethyl group-containing melamine compounds, carboxymethyl group-containing benzoguanamine compounds, carboxymethyl group-containing urea compounds, carboxymethyl group-containing glycoluril compounds, and carboxymethyl group-containing phenol compounds; (iv) epoxy compounds such as bisphenol A-based epoxy compounds, bisphenol F-based epoxy compounds, bisphenol S-based epoxy compounds, novolak resin-based epoxy compounds, resol resin-based epoxy compounds, and poly (hydroxystyrene) -based epoxy compounds. .

As the acid crosslinking agent (G), further, a compound having a phenolic hydroxyl group and a compound and a resin in which the crosslinkable group is introduced into the acidic functional group in the alkali-soluble resin and imparted crosslinkability can be used. In this case, the introduction rate of the crosslinkable group is preferably 5 to 100 mol%, more preferably 10 to 60 mol%, and even more preferably, based on the compound having a phenolic hydroxyl group and the total acidic functional group in the alkali-soluble resin. It is adjusted to 15 to 40 mol%. When the introduction rate of the crosslinkable group is within the above range, a crosslinking reaction is sufficiently caused, and a decrease in the residual film rate, swelling of the pattern, and meandering are avoided, which is preferable.

In the resist composition of the present embodiment, the acid crosslinking agent (G) is preferably an alkoxyalkylated urea compound or a resin thereof, or an alkoxyalkylated glycoluril compound or a resin thereof. Particularly preferred acid crosslinking agents (G) include compounds represented by the following formulas (8-1) to (8-3) and alkoxymethylated melamine compounds (acid crosslinking agents (G1)).

[Formula 26]

(In the formulas (8-1) to (8-3), R ⁷ each independently represents a hydrogen atom, an alkyl group or an acyl group; R ⁸ to R ¹¹ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group or an alkoxy group. X ² represents a single bond, a methylene group, or an oxygen atom.)

The alkyl group represented by R ⁷ is preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and is not particularly limited, and examples thereof include a methyl group, an ethyl group, and a propyl group. The acyl group represented by R ⁷ is preferably 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, and is not particularly limited, and examples thereof include an acetyl group and a propionyl group. The alkyl group represented by R ⁸ to R ¹¹ is preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and is not particularly limited, and examples thereof include a methyl group, an ethyl group, and a propyl group. The alkoxyl group represented by R ⁸ to R ¹¹ is preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, and a propoxy group. X ² is preferably a single bond or a methylene group. R ⁷ to R ¹¹ and X ² may be substituted with an alkyl group such as a methyl group or an ethyl group, an alkoxy group such as a methoxy group or an ethoxy group, a hydroxyl group, or a halogen atom. The plurality of R ⁷ , R ⁸ to R ¹¹ may be the same or different, respectively.

Although it does not specifically limit as a compound represented by Formula (8-1) specifically, For example, the compound etc. which are shown below are mentioned.

[Formula 27]

It is not specifically limited as a compound represented by Formula (8-2), For example, N, N, N, N-tetra (methoxymethyl) glycoluril, N, N, N, N-tetra (Ethoxymethyl) glycoluril, N, N, N, N-tetra (n-propoxymethyl) glycoluril, N, N, N, N-tetra (isopropoxymethyl) glycoluril, N, N, N And N-tetra (n-butoxymethyl) glycoluril, N, N, N, N-tetra (t-butoxymethyl) glycoluril, and the like. Of these, N, N, N, N-tetra (methoxymethyl) glycoluril is particularly preferable.

Although it does not specifically limit as a compound represented by Formula (8-3) specifically, For example, the compound etc. which are shown below are mentioned.

[Formula 28]

The alkoxymethylated melamine compound is not particularly limited, but, for example, N, N, N, N, N, N-hexa (methoxymethyl) melamine, N, N, N, N, N, N- Hexa (ethoxymethyl) melamine, N, N, N, N, N, N-hexa (n-propoxymethyl) melamine, N, N, N, N, N, N-hexa (isopropoxymethyl) melamine , N, N, N, N, N, N-hexa (n-butoxymethyl) melamine, N, N, N, N, N, N-hexa (t-butoxymethyl) melamine, and the like. Among them, N, N, N, N, N, N-hexa (methoxymethyl) melamine is particularly preferable.

Although the acid crosslinking agent (G1) is not particularly limited, for example, after introducing a methylol group by condensation reaction of a urea compound or a glycoluril compound, and formalin, further, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, etc. It is obtained by etherifying with lower alcohols, and then cooling the reaction solution to recover the precipitated compound or its resin. Moreover, the said acid crosslinking agent (G1) can also be obtained as a commercial item, such as CYMEL (trade name, Mitsui-Cyanamid, Ltd.) and NIKALAC (made by Sanwa Chemical Industrial Co., Ltd.).

In addition, as another particularly preferred acid crosslinking agent (G), the molecule has 1 to 6 benzene rings, has 2 or more hydroxyalkyl groups and / or alkoxyalkyl groups in the molecule, and the hydroxyalkyl groups and / or alkoxyalkyl groups are And phenol derivatives bound to any one benzene ring (acid crosslinking agent (G2)). As the acid crosslinking agent (G), preferably, the molecular weight is 1500 or less, and has 1 to 6 benzene rings in the molecule, and has 2 or more of hydroxyalkyl groups and / or alkoxyalkyl groups, and this hydroxyalkyl group and / or alkoxyalkyl group And phenol derivatives formed by bonding to any one of the benzene rings or a plurality of benzene rings.

As the hydroxyalkyl group bonded to the benzene ring, a hydroxyalkyl group having 1 to 6 carbon atoms such as a hydroxymethyl group, 2-hydroxyethyl group, and 2-hydroxy-1-propyl group is preferable. As the alkoxyalkyl group bonded to the benzene ring, an alkoxyalkyl group having 2 to 6 carbon atoms is preferable. Specifically, methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, isopropoxymethyl group, n-butoxymethyl group, isobutoxymethyl group, sec-butoxymethyl group, t-butoxymethyl group, 2-methoxyethyl group or 2-methoxy-1-propyl group is preferred.

Among these phenol derivatives, particularly preferred ones are listed below.

[Formula 29]

[Formula 30]

[Formula 31]

[Formula 32]

[Formula 33]

[Formula 34]

In the formula, L ¹ to L ⁸ may be the same or different, and each independently represents a hydroxymethyl group, a methoxymethyl group, or an ethoxymethyl group. The phenol derivative having a hydroxymethyl group can be obtained by reacting a phenolic compound having no corresponding hydroxymethyl group (a compound in which L ¹ to L ⁸ in the above formula is a hydrogen atom) and formaldehyde under a base catalyst. At this time, in order to prevent resination or gelation, it is preferable to carry out the reaction temperature at 60 ° C or lower. Specifically, it can be synthesized by the method described in Japanese Patent Laid-Open H6-282067, Japanese Patent Laid-Open H7-64285, and the like.

A phenol derivative having an alkoxymethyl group can be obtained by reacting a corresponding phenol derivative having a hydroxymethyl group with an alcohol under an acid catalyst. At this time, in order to prevent resination or gelation, it is preferable to carry out the reaction temperature at 100 ° C or lower. Specifically, it can be synthesized by the method described in EP632003A1 or the like.

The phenol derivative having a hydroxymethyl group and / or an alkoxymethyl group synthesized in this way is preferable from the viewpoint of stability during storage. The phenol derivative having an alkoxymethyl group is particularly preferred from the viewpoint of stability during storage. The acid crosslinking agent (G2) may be used alone or in combination of two or more.

Moreover, although it does not specifically limit as another especially preferable acid crosslinking agent (G), For example, the compound which has at least 1 alpha-hydroxyisopropyl group is mentioned (acid crosslinking agent (G3)). As long as it has an α-hydroxyisopropyl group, the structure is not particularly limited. Further, the hydrogen atom of the hydroxyl group in the α-hydroxyisopropyl group is one or more acid dissociable groups (R-COO- group, R-SO ₂ -group, etc., R is a linear hydrocarbon group having 1 to 12 carbon atoms) , Represents a substituent selected from the group consisting of a cyclic hydrocarbon group having 3 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a 1-branched alkyl group having 3 to 12 carbon atoms, and an aromatic hydrocarbon group having 6 to 12 carbon atoms). have. The compound having the α-hydroxyisopropyl group is not particularly limited, but, for example, a substituted or unsubstituted aromatic-based compound containing at least one α-hydroxyisopropyl group, a diphenyl compound, a naphthalene compound, and furan And 1 or 2 or more types, such as a compound. Although not specifically limited, For example, the compound represented by the following general formula (9-1) (hereinafter referred to as "benzene-based compound (1)"), represented by the following general formula (9-2) Compound (hereinafter referred to as "diphenyl-based compound (2)"), a compound represented by the following general formula (9-3) (hereinafter referred to as "naphthalene-based compound (3")), and the following general formula (9 And compounds represented by -4) (hereinafter referred to as "furan-based compounds (4)") and the like.

[Formula 35]

In the general formulas (9-1) to (9-4), A ² each independently represents an α-hydroxyisopropyl group or a hydrogen atom, and at least one A ² is an α-hydroxyisopropyl group. to be. In addition, in General Formula (9-1), R ⁵¹ represents a hydrogen atom, a hydroxyl group, a straight-chain or branched alkylcarbonyl group having 2 to 6 carbon atoms, or a straight-chain or branched alkoxycarbonyl group having 2 to 6 carbon atoms. . Moreover, in general formula (9-2), R ⁵² represents a single bond, a C1-C5 linear or branched alkylene group, -O-, -CO- or -COO-. In addition, in General Formula (9-4), R ⁵³ and R ⁵⁴ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms.

Although it does not specifically limit specifically, as said benzene type compound (1), For example, alpha-hydroxyisopropylbenzene, 1,3-bis (alpha-hydroxyisopropyl) benzene, 1,4-bis ( α-hydroxyisopropyl, such as α-hydroxyisopropyl) benzene, 1,2,4-tris (α-hydroxyisopropyl) benzene, 1,3,5-tris (α-hydroxyisopropyl) benzene, etc. Benzenes; 3-α-hydroxyisopropylphenol, 4-α-hydroxyisopropylphenol, 3,5-bis (α-hydroxyisopropyl) phenol, 2,4,6-tris (α-hydroxyisopropyl) Α-hydroxyisopropylphenols such as phenol; 3-α-hydroxyisopropylphenyl-methylketone, 4-α-hydroxyisopropylphenyl-methylketone, 4-α-hydroxyisopropylphenyl-ethylketone, 4-α-hydroxyisopropylphenyl-n -Propyl ketone, 4-α-hydroxyisopropylphenyl-isopropyl ketone, 4-α-hydroxyisopropylphenyl-n-butyl ketone, 4-α-hydroxyisopropylphenyl-t-butyl ketone, 4- α-hydroxyisopropylphenyl-n-pentylketone, 3,5-bis (α-hydroxyisopropyl) phenyl-methylketone, 3,5-bis (α-hydroxyisopropyl) phenyl-ethylketone, 2 Α-hydroxyisopropylphenyl-alkyl ketones such as, 4,6-tris (α-hydroxyisopropyl) phenyl-methyl ketone; 3-α-hydroxyisopropyl benzoate, 4-α-hydroxyisopropyl benzoate, 4-α-hydroxyisopropyl benzoate, 4-α-hydroxyisopropyl benzoate n-propyl, 4-α- Isopropyl hydroxyisopropyl benzoate, n-butyl 4-α-hydroxyisopropyl benzoate, t-butyl 4-α-hydroxyisopropyl benzoate, n-pentyl 4-α-hydroxyisopropyl benzoate, 3,5 4-, such as methyl bis (α-hydroxyisopropyl) benzoate, ethyl 3,5-bis (α-hydroxyisopropyl) benzoate, methyl 2,4,6-tris (α-hydroxyisopropyl) benzoate, etc. and α-hydroxyisopropyl benzoic acid alkyls.

Moreover, it is although it does not specifically limit as said diphenyl type compound (2) specifically, For example, 3- alpha-hydroxy isopropyl biphenyl, 4- alpha-hydroxy isopropyl biphenyl, 3, 5- Bis (α-hydroxyisopropyl) biphenyl, 3,3'-bis (α-hydroxyisopropyl) biphenyl, 3,4'-bis (α-hydroxyisopropyl) biphenyl, 4,4 ' -Bis (α-hydroxyisopropyl) biphenyl, 2,4,6-tris (α-hydroxyisopropyl) biphenyl, 3,3 ', 5-tris (α-hydroxyisopropyl) biphenyl, 3,4 ', 5-tris (α-hydroxyisopropyl) biphenyl, 2,3', 4,6, -tetrakis (α-hydroxyisopropyl) biphenyl, 2,4,4 ', 6 , -Tetrakis (α-hydroxyisopropyl) biphenyl, 3,3 ', 5,5'-tetrakis (α-hydroxyisopropyl) biphenyl, 2,3', 4,5 ', 6- Α-hydroxyisopropylbiphenyl such as pentakis (α-hydroxyisopropyl) biphenyl, 2,2 ′, 4,4 ′, 6,6′-hexakis (α-hydroxyisopropyl) biphenyl Ryu; 3-α-hydroxyisopropyldiphenylmethane, 4-α-hydroxyisopropyldiphenylmethane, 1- (4-α-hydroxyisopropylphenyl) -2-phenylethane, 1- (4-α- Hydroxyisopropylphenyl) -2-phenylpropane, 2- (4-α-hydroxyisopropylphenyl) -2-phenylpropane, 1- (4-α-hydroxyisopropylphenyl) -3-phenylpropane, 1- (4-α-hydroxyisopropylphenyl) -4-phenylbutane, 1- (4-α-hydroxyisopropylphenyl) -5-phenylpentane, 3,5-bis (α-hydroxyisopropyl) Diphenylmethane, 3,3'-bis (α-hydroxyisopropyl) diphenylmethane, 3,4'-bis (α-hydroxyisopropyl) diphenylmethane, 4,4'-bis (α-hydroxy Hydroxyisopropyl) diphenylmethane, 1,2-bis (4-α-hydroxyisopropylphenyl) ethane, 1,2-bis (4-α-hydroxypropylphenyl) propane, 2,2-bis (4 -α-hydroxypropylphenyl) propane, 1,3-bis (4-α-hydroxypropylphenyl) propane, 2,4,6-tris (α-hydroxyisopropyl) diphenylmethane, 3,3 ' , 5-tris (α-hydroxyisopropyl) diphenylmethane, 3,4 ', 5-tris (α-hydroxyisopropyl) diphenylmethane, 2,3', 4,6-tetrakis (α- Hydroxyisopropyl) diphenylmethane, 2,4,4 ', 6-tetrakis (α-hydroxyisopropyl) diphenylmethane, 3,3', 5,5'-tetrakis (α-hydroxyiso Propyl) diphenylmethane, 2,3 ', 4,5', 6-pentakis (α-hydroxyisopropyl) diphenylmethane, 2,2 ', 4,4', 6,6'-hexakis ( α-hydroxyisopropyldiphenyl alkanes such as α-hydroxyisopropyl) diphenylmethane; 3-α-hydroxyisopropyldiphenyl ether, 4-α-hydroxyisopropyldiphenyl ether, 3,5 -Bis (α-hydroxyisopropyl) diphenyl ether, 3,3'-bis (α-hydroxyisopropyl) diphenyl ether, 3,4'-bis (α-hydroxyisopropyl) diphenyl ether, 4,4'-bis (α-hydroxyisopropyl) diphenyl ether, 2,4,6-tris (α-hydroxyisopropyl) diphenyl ether, 3,3 ', 5-tris (α-hydroxy Isopropyl) diphenyl ether, 3,4 ', 5-tris (α-hydroxyisopropyl) diphenyl ether, 2,3', 4,6-te Trakis (α-hydroxyisopropyl) diphenyl ether, 2,4,4 ', 6-tetrakis (α-hydroxyisopropyl) diphenyl ether, 3,3', 5,5'-tetrakis ( α-hydroxyisopropyl) diphenyl ether, 2,3 ', 4,5', 6-pentakis (α-hydroxyisopropyl) diphenyl ether, 2,2 ', 4,4', 6,6 Α-hydroxyisopropyl diphenyl ethers such as' -hexakis (α-hydroxyisopropyl) diphenyl ether; 3-α-hydroxyisopropyldiphenylketone, 4-α-hydroxyisopropyldiphenylketone, 3,5-bis (α-hydroxyisopropyl) diphenylketone, 3,3'-bis (α- Hydroxyisopropyl) diphenylketone, 3,4'-bis (α-hydroxyisopropyl) diphenylketone, 4,4'-bis (α-hydroxyisopropyl) diphenylketone, 2,4,6 -Tris (α-hydroxyisopropyl) diphenylketone, 3,3 ', 5-tris (α-hydroxyisopropyl) diphenylketone, 3,4', 5-tris (α-hydroxyisopropyl) Diphenylketone, 2,3 ', 4,6-tetrakis (α-hydroxyisopropyl) diphenylketone, 2,4,4', 6-tetrakis (α-hydroxyisopropyl) diphenylketone, 3,3 ', 5,5'-tetrakis (α-hydroxyisopropyl) diphenylketone, 2,3', 4,5 ', 6-pentakis (α-hydroxyisopropyl) diphenylketone, Α-hydroxyisopropyl diphenyl ketones such as 2,2 ', 4,4', 6,6'-hexakis (α-hydroxyisopropyl) diphenyl ketone; 3-α-hydroxyisopropylbenzoate phenyl, 4-α-hydroxyisopropylbenzoate phenyl, benzoic acid3-α-hydroxyisopropylphenyl, benzoic acid4-α-hydroxyisopropylphenyl, 3,5-bis ( α-hydroxyisopropyl) benzoic acid phenyl, 3-α-hydroxyisopropylbenzoic acid3-α-hydroxyisopropylphenyl, 3-α-hydroxyisopropylbenzoic acid4-α-hydroxyisopropylphenyl, 4- α-hydroxyisopropylbenzoic acid 3-α-hydroxyisopropylphenyl, 4-α-hydroxyisopropylbenzoic acid4-α-hydroxyisopropylphenyl, benzoic acid 3,5-bis (α-hydroxyisopropyl) Phenyl, 2,4,6-tris (α-hydroxyisopropyl) benzoic acid phenyl, 3,5-bis (α-hydroxyisopropyl) benzoic acid 3-α-hydroxyisopropylphenyl, 3,5-bis ( α-hydroxyisopropyl) benzoic acid 4-α-hydroxyisopropylphenyl, 3-α-hydroxyisopropylbenzoic acid 3,5-bis (α-hydroxyisopropyl) phenyl, 4-α-hydroxyisopropyl 3,5-bis (α-hydroxyisopropyl) phenyl benzoate, 2,4,6-tris (α-hydroxyisopropyl) phenyl benzoate, 2,4,6-tris (α-hydroxyisopropyl) benzoic acid 3-α-hydroxyisopropylphenyl, 2,4,6-tris (α-hydroxyisopropyl) benzoic acid 4-α-hydroxyisopropylphenyl, 3,5-bis (α-hydroxyisopropyl) benzoic acid 3,5-bis (α-hydroxyisopropyl) phenyl, 3-α-hydroxyisopropylbenzoic acid 2,4,6-tris (α-hydroxyisopropyl) phenyl, 4-α-hydroxyisopropylbenzoic acid 2,4,6-tris (α-hydroxyisopropyl) phenyl, 2,4,6-tris (α-hydroxyisopropyl) benzoic acid 3,5-bis (α-hydroxyisopropyl) phenyl, 3, 5-bis (α-hydroxyisopropyl) benzoic acid 2,4,6-tris (α-hydroxyisopropyl) phenyl, 2,4,6-tris (α-hydroxyisopropyl) benzoic acid 2,4,6 And α-hydroxyisopropyl benzoic acid phenyls such as tris (α-hydroxyisopropyl) phenyl.

Further, the naphthalene-based compound (3) is not specifically limited, but is, for example, 1- (α-hydroxyisopropyl) naphthalene, 2- (α-hydroxyisopropyl) naphthalene, 1,3 -Bis (α-hydroxyisopropyl) naphthalene, 1,4-bis (α-hydroxyisopropyl) naphthalene, 1,5-bis (α-hydroxyisopropyl) naphthalene, 1,6-bis (α- Hydroxyisopropyl) naphthalene, 1,7-bis (α-hydroxyisopropyl) naphthalene, 2,6-bis (α-hydroxyisopropyl) naphthalene, 2,7-bis (α-hydroxyisopropyl) Naphthalene, 1,3,5-tris (α-hydroxyisopropyl) naphthalene, 1,3,6-tris (α-hydroxyisopropyl) naphthalene, 1,3,7-tris (α-hydroxyisopropyl) ) Naphthalene, 1,4,6-tris (α-hydroxyisopropyl) naphthalene, 1,4,7-tris (α-hydroxyisopropyl) naphthalene, 1,3,5,7-tetrakis (α-) And hydroxyisopropyl) naphthalene.

Further, the furan-based compound (4) is not particularly limited, but for example, 3- (α-hydroxyisopropyl) furan, 2-methyl-3- (α-hydroxyisopropyl) furan , 2-methyl-4- (α-hydroxyisopropyl) furan, 2-ethyl-4- (α-hydroxyisopropyl) furan, 2-n-propyl-4- (α-hydroxyisopropyl) furan , 2-isopropyl-4- (α-hydroxyisopropyl) furan, 2-n-butyl-4- (α-hydroxyisopropyl) furan, 2-t-butyl-4- (α-hydroxyiso Propyl) furan, 2-n-pentyl-4- (α-hydroxyisopropyl) furan, 2,5-dimethyl-3- (α-hydroxyisopropyl) furan, 2,5-diethyl-3- ( α-hydroxyisopropyl) furan, 3,4-bis (α-hydroxyisopropyl) furan, 2,5-dimethyl-3,4-bis (α-hydroxyisopropyl) furan, 2,5-di And ethyl-3,4-bis (α-hydroxyisopropyl) furan.

As the acid crosslinking agent (G3), a compound having two or more free α-hydroxyisopropyl groups is preferable, and the benzene-based compound (1) having two or more α-hydroxyisopropyl groups and an α-hydroxyisopropyl group The diphenyl-based compound (2) having two or more, and the naphthalene-based compound (3) having two or more α-hydroxyisopropyl groups are more preferable, and α-hydroxyisopropyl having two or more α-hydroxyisopropyl groups Biphenyls and a naphthalene-based compound (3) having two or more α-hydroxyisopropyl groups are particularly preferred.

The acid crosslinking agent (G3) is usually a method of hydrolysis after methylation by reacting a Grignard reagent such as CH ₃ MgBr with a acetyl group-containing compound such as 1,3-diacetylbenzene, followed by methylation. It can be obtained by oxidizing an isopropyl group-containing compound such as diisopropylbenzene with oxygen or the like to produce a peroxide and then reducing it.

In the resist composition of the present embodiment, the content of the acid crosslinking agent (G) is preferably 0.5 to 49 parts by mass, more preferably 0.5 to 40 parts by mass, based on 100 parts by mass of the total content of components other than the solvent. ~ 30 parts by mass is more preferable, and 2 to 20 parts by mass is particularly preferable. When the content of the acid crosslinking agent (G) is greater than or equal to the above lower limit, the effect of suppressing the solubility of the resist film in the alkali developer is improved, and it is possible to suppress the residual film ratio from being lowered or the pattern swelling or meandering. On the other hand, when the content of the acid crosslinking agent (G) is less than or equal to the above upper limit, it is preferable from the viewpoint of suppressing the decrease in heat resistance as a resist.

In addition, the mixing ratio of at least one compound selected from the group consisting of the acid crosslinking agent (G1), the acid crosslinking agent (G2) and the acid crosslinking agent (G3) in the acid crosslinking agent (G) is not particularly limited, and the resist pattern It can be made into various ranges depending on the kind of substrate used at the time of formation.

In the total acid crosslinking agent component, the alkoxymethylated melamine compound and / or the compound represented by (9-1) to (9-3) is 50 to 99% by mass, preferably 60 to 99% by mass, more preferably It is preferable that it is 70-98 mass%, More preferably, it is 80-97 mass%. The alkoxymethylated melamine compound and / or the compounds represented by (9-1) to (9-3) are preferably 50% by mass or more of the total acid crosslinking agent component, so that the resolution can be improved. Or it is preferable because the compound represented by (9-1) to (9-3) is 99% by mass or less of the total acid crosslinking agent component, and is easily formed into a rectangular cross-sectional shape as a pattern cross-sectional shape.

(Acid diffusion control agent (E))

It is preferable that the resist composition of this embodiment further contains an acid diffusion control agent (E). The acid diffusion control agent (E) has an effect of controlling the diffusion of the acid generated from the acid generator in the resist film by irradiation with radiation to prevent an undesirable chemical reaction in the unexposed region. By using such an acid diffusion control agent (E), the storage stability of the resist composition is improved. In addition, the resolution is improved, and the change in the line width of the resist pattern due to the variation in the mounting time before irradiation and the mounting time after irradiation can be suppressed, so that the process stability is very excellent. The acid diffusion control agent (E) is not particularly limited, and examples thereof include radioactive decomposition basic compounds such as a nitrogen atom-containing basic compound, a basic sulfonium compound, and a basic iodonium compound. The acid diffusion control agent (E) may be used alone or in combination of two or more.

The acid diffusion control agent (E) is not particularly limited, and examples thereof include a nitrogen-containing organic compound, a basic compound decomposed by exposure, and the like. Although it does not specifically limit as said nitrogen-containing organic compound, For example, the compound represented by the following general formula (10) (hereinafter referred to as "nitrogen-containing compound (I)"), and two nitrogen atoms in the same molecule Diamino compound (hereinafter referred to as "nitrogen compound (II)"), polyamino compound or polymer having three or more nitrogen atoms (hereinafter referred to as "nitrogen compound (III)"), containing amide groups And compounds, urea compounds, and nitrogen-containing heterocyclic compounds. Moreover, the acid diffusion control agent (E) may be used alone or in combination of two or more.

[Formula 36]

In the general formula (10), R ⁶¹ , R ⁶² and R ⁶³ each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group, an aryl group or an aralkyl group. Further, the alkyl group, aryl group, or aralkyl group may be unsubstituted or substituted with a hydroxyl group or the like. Here, although it does not specifically limit as said linear, branched, or cyclic alkyl group, For example, the thing of C1-C15, Preferably it is 1-10. Although it does not specifically limit as a specific example of the said linear, branched, or cyclic alkyl group, For example, For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl Group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, texyl group, n-heptyl group, n-octyl group, n-ethylhexyl group, n-nonyl group, n-decyl group, etc. Can be heard. Moreover, although it does not specifically limit as said aryl group, For example, what has 6 to 12 carbon atoms is mentioned, Specifically, although it is not specifically limited, For example, a phenyl group, a tolyl group, a xylyl group, a cumenyl group And 1-naphthyl groups. Moreover, although it does not specifically limit as said aralkyl group, For example, what has 7-19 carbon atoms, Preferably it is 7-13, Specifically, although it is not specifically limited, For example, a benzyl group, and an α-methylbenzyl group, a phenethyl group, and a naphthylmethyl group.

Although it does not specifically limit specifically, as said nitrogen-containing compound (I), For example, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-dodecyl Mono (cyclo) alkylamines such as amine and cyclohexylamine; Di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, methyl di (cyclo) alkylamines such as -n-dodecylamine, di-n-dodecylmethyl, cyclohexylmethylamine, and dicyclohexylamine; Triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n- Tri (cyclo) alkylamines such as nonylamine, tri-n-decylamine, dimethyl-n-dodecylamine, di-n-dodecylmethylamine, dicyclohexylmethylamine, and tricyclohexylamine; Alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine; Aromatics such as aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine, and 1-naphthylamine And amines.

Although it does not specifically limit specifically, as said nitrogen-containing compound (II), For example, ethylenediamine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetra Keith (2-hydroxypropyl) ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone , 4,4'-diaminodiphenylamine, 2,2-bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2- (4-amino Phenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl) -2- (4-hydroxyphenyl) propane, 1,4-bis [1- (4-aminophenyl) -1 -Methylethyl] benzene, 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene, and the like.

Although it does not specifically limit specifically, as said nitrogen-containing compound (III), For example, polymers of polyethyleneimine, polyallylamine, N- (2-dimethylaminoethyl) acrylamide, etc. are mentioned.

Although it does not specifically limit as said amide group containing compound specifically, For example, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethyl And acetamide, propionamide, benzamide, pyrrolidone, and N-methylpyrrolidone.

Although it does not specifically limit specifically, as said urea compound, For example, Urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1, 3-diphenylurea, tri-n-butylthiourea, etc. are mentioned.

Although it does not specifically limit as said nitrogen-containing heterocyclic compound specifically, For example, imidazole, benzimidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, 2-phenylbenzimi Imidazoles such as dazol; Pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinic acid amide, quinoline, Pyridines such as 8-oxyquinoline and acridine; And, pyrazine, pyrazole, pyridazine, quinoxaline, purine, pyrrolidine, piperidine, morpholine, 4-methylmorpholine, piperazine, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] Octane and the like.

Moreover, although it does not specifically limit as said radiation-decomposable basic compound, For example, the sulfonium compound represented by the following general formula (11-1), the iodonium compound represented by the following general formula (11-2), etc. Can be heard.

[Formula 37]

[Formula 38]

In the general formulas (11-1) and (11-2), R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ and R ⁷⁵ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms. It represents a real group, a hydroxyl group, or a halogen atom. Z ^- is ^{HO -, R-COO - (} . Where, R represents an alkaryl group having 1 to 6 carbon atoms alkyl group, having 6 to 11 carbon atoms or an aryl group of 7-12) or the following general formula (11-3) :

[Formula 39]

It represents the anion represented by.

Although it is not specifically limited as said radioactive decomposition basic compound, For example, triphenylsulfonium hydrooxide, triphenylsulfonium acetate, triphenylsulfonium salicylate, diphenyl-4-hydroxyphenylsulfonium Hydrooxide, diphenyl-4-hydroxyphenylsulfonium acetate, diphenyl-4-hydroxyphenylsulfonium salicylate, bis (4-t-butylphenyl) iodonium hydrooxide, bis (4-t-butyl Phenyl) iodonium acetate, bis (4-t-butylphenyl) iodonium hydrooxide, bis (4-t-butylphenyl) iodonium acetate, bis (4-t-butylphenyl) iodonium salicylate, 4- t-butylphenyl-4-hydroxyphenyl iodonium hydrooxide, 4-t-butylphenyl-4-hydroxyphenyl iodonium acetate, 4-t-butylphenyl-4-hydroxyphenyl iodonium salicylate, etc. Can be lifted.

In the resist composition of the present embodiment, the content of the acid diffusion control agent (E) is preferably 0.001 to 49 parts by mass, more preferably 0.01 to 10 parts by mass, with respect to 100 parts by mass of the total content of components other than the solvent. , 0.01 to 5 parts by mass is more preferable, and 0.01 to 3 parts by mass is particularly preferable. When the content of the acid diffusion control agent (E) is within the above range, deterioration in resolution, pattern shape and dimensional fidelity can be prevented. In addition, if the content of the acid diffusion control agent (E) is within the above range, the shape of the upper portion of the pattern does not deteriorate even if the mounting time from electron beam irradiation to radiation and heating is long. Moreover, when content of this acid diffusion control agent (E) is 10 mass parts or less, the fall of sensitivity, the developability of an unexposed part, etc. can be prevented. In addition, by using such an acid diffusion control agent, the storage stability of the resist composition is improved, and the resolution is improved, and the line width change of the resist pattern due to variation in the mounting time before irradiation and the mounting time after irradiation is suppressed. It is possible to achieve excellent process stability.

(Other ingredients (F))

In the resist composition of the present embodiment, as long as it does not impair the object of the present invention, if necessary, as other component (F), a dissolution accelerator, a dissolution control agent, a sensitizer, a surfactant and an organic carboxylic acid or phosphorus oxo acid or Various additives, such as derivatives, can be contained 1 type (s) or 2 or more types.

(1) Dissolution accelerator

The low-molecular-weight dissolution accelerator is a component having a function of increasing the solubility and appropriately increasing the dissolution rate of the compound during development when the solubility of the compound represented by the formula (1) in the developer is too low. It can be used in a range that does not impair the effects of the invention. Although it does not specifically limit as said dissolution accelerator, For example, low molecular weight phenolic compounds are mentioned, Specifically, bisphenols, tris (hydroxyphenyl) methane, etc. are mentioned, for example. These dissolution accelerators may be used alone or in combination of two or more.

In the resist composition of the present embodiment, the content of the dissolution accelerator is appropriately adjusted depending on the type of the resist substrate to be used, but is preferably 0 to 49 parts by mass with respect to 100 parts by mass of the total content of components other than the solvent. ~ 5 parts by mass is more preferable, 0 to 1 part by mass is more preferable, and 0 parts by mass is particularly preferable.

(2) Dissolution control agent

The dissolution control agent is a component having a function of appropriately reducing the dissolution rate during development by controlling the solubility when the compound represented by the formula (1) has too high solubility in the developer. As such a dissolution control agent, it is preferable that the resist film is not chemically changed in the process of firing, irradiation, development, and the like.

Although it does not specifically limit as a dissolution control agent, For example, aromatic hydrocarbons, such as phenanthrene, anthracene, and acenaphthene; Ketones such as acetophenone, benzophenone and phenylnaphthyl ketone; And sulfones such as methylphenyl sulfone, diphenyl sulfone, and dinaphthyl sulfone. These dissolution control agents may be used alone or in combination of two or more.

In the resist composition of the present embodiment, the content of the dissolution control agent is appropriately adjusted depending on the type of the resist substrate to be used, but 0 to 49 parts by mass is preferable with respect to 100 parts by mass of the total content of components other than the solvent. ~ 5 parts by mass is more preferable, 0 to 1 part by mass is more preferable, and 0 parts by mass is particularly preferable.

(3) sensitizer

The sensitizer is a component that absorbs the energy of the irradiated radiation, transmits the energy to the acid generator (C), thereby increasing the amount of acid generated, and improving the sensitivity of the appearance of the resist. The sensitizer is not particularly limited, and examples thereof include benzophenones, biacetyls, pyrenes, phenothiazines, and fluorenes. These sensitizers may be used alone or in combination of two or more.

In the resist composition of the present embodiment, the content of the sensitizer is appropriately adjusted depending on the type of the resist substrate to be used, but 0 to 49 parts by mass is preferable with respect to 100 parts by mass of the total content of components other than the solvent. ~ 5 parts by mass is more preferable, 0 to 1 part by mass is more preferable, and 0 parts by mass is particularly preferable.

(4) surfactant

The surfactant is a component having an action of improving the coatability, striation, and developability of the resist composition of the present embodiment. The surfactant may be either anionic, cationic, nonionic or amphoteric. Preferred surfactants are nonionic surfactants. The nonionic surfactant has good affinity with a solvent used for the production of a resist composition, and is more effective. The nonionic surfactant is not particularly limited, and examples thereof include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, and higher fatty acid diesters of polyethylene glycol. Although it is not specifically limited as a commercial item of a nonionic surfactant, For example, EFTOP (made by Jemco Co., Ltd), MEGAFAC (made by DIC Corporation), FLUORAD (made by Sumitomo 3M Limited), Asahi, for example with the following brand names Guard, SURFLON (above, manufactured by Ashi Glass Co., Ltd.), PEPOL (manufactured by TOHO Chemical Industry Co., Ltd.), KP (Shin-Etsu Chemical Co., Ltd.), POLYFLOW (Kyoeisha Yushi Kagaku Kogyo Co ., Ltd.).

In the resist composition of the present embodiment, the content of the surfactant is appropriately adjusted depending on the type of the resist substrate to be used, but 0 to 49 parts by mass is preferable with respect to 100 parts by mass of the total content of components other than the solvent. ~ 5 parts by mass is more preferable, 0 to 1 part by mass is more preferable, and 0 parts by mass is particularly preferable.

(5) Organic carboxylic acids or phosphorus oxo acids or derivatives thereof

The resist composition of the present embodiment may contain an organic carboxylic acid or an oxo acid of phosphorus or a derivative thereof as an optional component for the purpose of preventing deterioration in sensitivity or improving resist pattern shape, stabilization, and the like. Moreover, the organic carboxylic acid or the oxo acid of phosphorus or its derivative (s) can be used together with an acid diffusion control agent, or can be used alone. Although it does not specifically limit as organic carboxylic acid, For example, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid, etc. are suitable. Examples of phosphorus oxo acids or derivatives thereof include phosphoric acid such as phosphoric acid, di-n-butyl phosphate, diphenyl phosphate or derivatives of these esters, phosphonic acid, dimethyl phosphonate, di-n-butyl phosphonate, Phosphonic acids such as phenylphosphonic acid, diphenyl phosphonate, dibenzyl phosphonate, or derivatives of these esters; phosphinic acids such as phosphinic acid and phenylphosphinic acid; and derivatives of these esters. Phosphonic acid is preferred.

The organic carboxylic acid or phosphorus oxo acid or a derivative thereof may be used alone or in combination of two or more.

In the resist composition of the present embodiment, the content of the organic carboxylic acid or phosphorus oxo acid or its derivative is appropriately adjusted depending on the type of the resist substrate to be used, but with respect to 100 parts by mass of the total content of components other than the above solvent, 0 -49 parts by mass is preferable, 0 to 5 parts by mass is more preferable, 0 to 1 part by mass is more preferable, and 0 parts by mass is particularly preferable.

(6) Other additives

In addition, in the resist composition of the present embodiment, as long as it does not impair the object of the present invention, if necessary, the dissolution control agent, a sensitizer, and other additives other than surfactants and organic carboxylic acids or phosphorus oxo acids or derivatives thereof It can contain 1 type, or 2 or more types. Although it does not specifically limit as such an additive, For example, a dye, a pigment, an adhesion aid, etc. are mentioned. For example, when a dye or pigment is contained, a resist composition is preferable because it can visualize the latent image of the exposed portion and mitigate the effect of halation during exposure. In addition, when an adhesive aid is included, the resist composition is preferable because it can improve the adhesion to the substrate. Furthermore, examples of other additives include anti-halation agents, preservation stabilizers, antifoaming agents, and shape improving agents, and specifically, 4-hydroxy-4'-methylchalcone.

In the resist composition of the present embodiment, the total content of the other components (F) is preferably 0 to 49 parts by mass, more preferably 0 to 5 parts by mass, relative to 100 parts by mass of the total content of components other than the solvent, 0-1 mass part is more preferable, and 0 mass part is especially preferable.

The content ratio (mass%) of the resist base material (A) / acid generator (C) / acid crosslinking agent (G) / acid diffusion control agent (E) / other component (F) in the components other than the solvent is preferable. Preferably, 50.000 ~ 99.498 / 0.001 ~ 49.000 / 0.500 ~ 49.000 / 0.001 ~ 49.000 / 0.000 ~ 49.000, more preferably, 50.000 ~ 90.000 / 1.000 ~ 40.000 / 0.500 ~ 40.000 / 0.010 ~ 10.000 / 0.000 ~ 5.000, more preferably Preferably, 50.000 to 85.000 / 3.000 to 30.000 / 1.000 to 30.000 / 0.010 to 5.000 / 0.000 to 1.000, particularly preferably 50.000 to 70.000 / 10.000 to 25.000 / 2.000 to 20.000 / 0.010 to 3.000 / 0.000. The content ratio of each component other than the said solvent is selected from each range so that the sum may become 100 mass%. When the content ratio of each component other than the above solvent is within the above range, the resist composition is excellent in performances such as sensitivity, resolution, and developability.

[Method of manufacturing resist composition]

Although the resist composition of the present embodiment is not particularly limited, for example, in use, components other than the above-described solvents (resist base material, etc.) are dissolved in a solvent to form a uniform solution, and then, if necessary, for example For example, it can be produced by filtering with a filter having a pore diameter of about 0.2 μm.

Although it does not specifically limit as said solvent used for the manufacture of the resist composition of this embodiment, For example, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene Ethylene glycol monoalkyl ether acetates such as glycol mono-n-butyl ether acetate; Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, and propylene glycol mono-n-butyl ether acetate; Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether; Lactate esters such as methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate and n-amyl lactate; Aliphatic carboxylic acid esters such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, methyl propionate and ethyl propionate; 3-methoxypropionate methyl, 3-methoxypropionate ethyl, 3-ethoxypropionate methyl, 3-ethoxypropionate ethyl, 3-methoxy-2-methylmethyl propionate, 3-methoxybutyl acetate, 3-methyl- Other esters such as 3-methoxybutyl acetate, 3-methoxy-3-methylpropionate butyl, 3-methoxy-3-methylbutyrate, methyl acetoacetate, methyl pyruvate and ethyl pyruvate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone, and cyclohexanone; Amides such as N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone; and lactones such as γ-lactone. Among them, as the solvent, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate (PGEEA), propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether (PGEE), cyclohexanone, Ethyl lactate and N-methylpyrrolidone are preferred. Such a solvent can give a coating film of a uniform film thickness with few defects, and it is also easy to dissolve components (resist substrates, etc.) other than the above-mentioned solvent, and further, has less harmfulness to the human body. These solvents may be used alone or in combination of two or more.

The resist composition of this embodiment can contain a resin in the range which does not impair the objective of this invention. Although it does not specifically limit as resin, For example, novolak resin; Polyvinylphenols; Polyacrylic acid; Polyvinyl alcohol; Styrene-maleic anhydride; And a polymer containing acrylic acid, vinyl alcohol, or vinylphenol as a monomer unit; Or these derivatives etc. are mentioned. In the resist composition of the present embodiment, the content of the resin is appropriately adjusted depending on the type of resist substrate to be used, but per 100 parts by weight of the resist substrate is preferably 30 parts by weight or less, more preferably 10 parts by weight or less, further It is preferably 5 parts by weight or less, particularly preferably 0 parts by weight.

[Method of manufacturing resist pattern]

The manufacturing method of the resist pattern of this embodiment includes the process of apply | coating the said resist composition on a board | substrate, forming a resist film, the process of exposing the said resist film, and the process of developing the exposed resist film. The resist pattern can also be produced as an upper layer resist in a multi-layer process.

Hereinafter, the method of manufacturing the resist pattern of the present embodiment will be specifically described, but the method of manufacturing the resist pattern of the present embodiment is not limited to the following method. First, a resist film is formed by applying the above-described resist composition on a conventionally known substrate by applying means such as rotation coating, flexible coating, and roll coating. The conventionally known substrate is not particularly limited, and examples thereof include a substrate for an electronic component, and a predetermined wiring pattern formed thereon. More specifically, it is not particularly limited, and examples thereof include metal wafers such as silicon wafers, copper, chromium, iron, and aluminum, and glass substrates. The material of the wiring pattern is not particularly limited, and examples thereof include copper, aluminum, nickel, and gold. In addition, if necessary, inorganic and / or organic films may be provided on the substrate. Although it does not specifically limit as an inorganic type film, For example, the inorganic antireflection film (inorganic BARC) is mentioned. Although it does not specifically limit as an organic type film, For example, an organic antireflection film (organic BARC) is mentioned. Surface treatment such as a substrate for an electronic component or a predetermined wiring pattern formed thereon may be performed by hexamethylene disilazane or the like.

Subsequently, the coated substrate is heated, if necessary. The heating temperature varies depending on the composition of the resist composition, and the like, preferably 20 to 250 ° C, and more preferably 20 to 150 ° C. It is preferable in some cases that the adhesion of the resist to the substrate is improved by heating the substrate. Subsequently, the resist film is exposed to a desired pattern by any one radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet (EUV), X-ray, and ion beam. The exposure conditions and the like are appropriately selected depending on the composition of the resist composition and the like. In this embodiment, in order to stably form a fine pattern with high precision in exposure, it is preferable to heat the resist film after irradiation. The heating temperature varies depending on the composition of the resist composition, and the like, preferably 20 to 250 ° C, and more preferably 20 to 150 ° C.

Subsequently, by developing the exposed resist film with a developer, a predetermined resist pattern can be produced. As the developing solution, it is preferable to select a solvent having a solubility parameter (SP value) close to the compound represented by the formula (1) to be used. The developer is not particularly limited, and examples thereof include polar solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents, hydrocarbon solvents, and alkali aqueous solutions.

Although it does not specifically limit as a ketone system solvent, For example, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexa Paddy, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonyl acetone, ionone, diacetyl alcohol, acetylcarbinol, acetophenone And methyl naphthyl ketone, isophorone, and propylene carbonate.

Although it does not specifically limit as an ester solvent, For example, methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl Ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate , Ethyl lactate, butyl lactate, propyl lactate, and the like.

Although it does not specifically limit as an alcohol type solvent, For example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol (2-propanol), n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, Alcohols such as isobutyl alcohol, n-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl alcohol, n-octyl alcohol, n-decanol, and glycols such as ethylene glycol, diethylene glycol, and triethylene glycol Solvents, glycol ethers such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethylbutanol And solvents.

Although it does not specifically limit as an ether type solvent, For example, dioxane, tetrahydrofuran, etc. are mentioned other than the said glycol ether type solvent.

The amide-based solvent is not particularly limited, but, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1, 3-dimethyl-2-imidazolidinone and the like.

Although it does not specifically limit as a hydrocarbon type solvent, For example, aromatic hydrocarbon type solvents, such as toluene and xylene, and aliphatic hydrocarbon type solvents, such as pentane, hexane, octane, and decane, are mentioned.

A plurality of the solvents may be mixed, or within a range having performance, they may be mixed with a solvent or water other than the above. However, in order to sufficiently exhibit the effects of the present invention, the water content as a whole developer is preferably less than 70% by mass, more preferably less than 50% by mass, even more preferably less than 30% by mass, and more preferably less than 10% by mass. It is more preferable. Moreover, it is especially preferable that the said solvent does not contain moisture substantially. That is, the content of the organic solvent in the developer is preferably 30% by mass or more and 100% by mass or less, more preferably 50% by mass or more and 100% by mass or less, and more preferably 70% by mass or more and 100% by mass or less with respect to the total amount of the developer. More preferably, it is more preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less.

The alkali aqueous solution is not particularly limited, and for example, mono-, di- or trialkylamines, mono-, di- or trialkanolamines, heterocyclic amines, tetramethylammonium hydroxide (TMAH), choline And alkaline compounds.

In particular, the developer is a developer containing at least one solvent selected from the group consisting of a ketone-based solvent, an ester-based solvent, an alcohol-based solvent, an amide-based solvent, and an ether-based solvent, such as resolution or roughness of a resist pattern. It is desirable to improve the resist performance.

At 20 ° C, the vapor pressure of the developer is preferably 5 kPa or less, more preferably 3 kPa or less, and even more preferably 2 kPa or less. By setting the vapor pressure of the developer to 5 kPa or less, evaporation of the developer on the substrate or in the developing cup is suppressed, temperature uniformity in the wafer surface is improved, and as a result, dimensional uniformity in the wafer surface is improved.

Specific examples of the developer having a vapor pressure of 5 kPa or less are not particularly limited, but, for example, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone , Ketone-based solvents such as diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, and methyl isobutyl ketone; Butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxy Ester solvents such as butyl acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propyl formate, ethyl lactate, butyl lactate and propyl lactate; n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl alcohol, n-octyl Alcoholic solvents such as alcohol and n-decanol; Glycol-based solvents such as ethylene glycol, diethylene glycol, and triethylene glycol; Glycol ether solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and methoxymethylbutanol; Ether-based solvents such as tetrahydrofuran; Amide solvents of N-methyl-2-pyrrolidone, N, N-dimethylacetamide and N, N-dimethylformamide; Aromatic hydrocarbon-based solvents such as toluene and xylene; And aliphatic hydrocarbon-based solvents such as octane and decane.

Specific examples of the developer having a vapor pressure of 2 kPa or less, which is a more preferable range, are not particularly limited, but are, for example, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, Ketone solvents such as 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone and phenyl acetone; Butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxy Ester solvents such as butyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate and propyl lactate; Alcohols such as n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl alcohol, n-octyl alcohol, and n-decanol System solvents; Glycol-based solvents such as ethylene glycol, diethylene glycol, and triethylene glycol; Glycol ether solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and methoxymethylbutanol; Amide solvents of N-methyl-2-pyrrolidone, N, N-dimethylacetamide and N, N-dimethylformamide; Aromatic hydrocarbon-based solvents such as xylene; And aliphatic hydrocarbon-based solvents such as octane and decane.

An appropriate amount of a surfactant can be added to the developer as needed. Although it does not specifically limit as surfactant, For example, ionic or nonionic fluorine type and / or silicone type surfactant, etc. can be used. These fluorine and / or silicone-based surfactants are not particularly limited, but, for example, Japanese Patent Publication S62-36663, Japanese Patent Publication S61-226746, Japanese Patent Publication S61-226745, Japanese Patent Publication S62 -170950 publication, Japanese patent publication S63-34540 publication, Japanese patent publication H7-230165 publication, Japanese patent publication H8-62834 publication, Japanese patent publication H9-54432 publication, Japanese patent publication H9-5988 publication, U.S. Patent No. 5,520,520, U.S. Patent No. 5360692, U.S. Patent No. 5529881, U.S. Patent No. 5296330, U.S. Patent No. 5436098, U.S. Pat. The surfactant described in the specification of Patent No. 5824451 is mentioned, and it is preferably a nonionic surfactant. Although it does not specifically limit as a nonionic surfactant, It is more preferable to use a fluorochemical surfactant or a silicone surfactant.

The surfactant is used in an amount of preferably 0.001 to 5% by mass, more preferably 0.005 to 2% by mass, and even more preferably 0.01 to 0.5% by mass relative to the total amount of the developer.

Although it does not specifically limit as a developing method, For example, the method of immersing a board | substrate in a bath filled with a developer for a certain time (dipping method), the method of developing by stacking a developer on the surface of a board | substrate with surface tension and stopping for a certain time ( Paddle method), the method of spraying the developer on the surface of the substrate (spray method), the method of continuously drawing the developer while scanning the developer-derived nozzle at a constant speed on a rotating substrate (dynamic dispensing method), etc. Can be. The time for developing the pattern is not particularly limited, but is preferably 10 seconds to 90 seconds.

Further, after the developing step, a step of stopping the development may be performed while the developing solution is replaced with another solvent.

After the developing step, it is preferable to include a step (cleaning step) of cleaning the resist pattern using a rinse liquid containing an organic solvent.

The rinse liquid used in the washing step after the developing step is not particularly limited as long as the resist pattern cured by crosslinking is not dissolved, and, for example, a solution or water containing a general organic solvent can be used. As the rinse solution, it is preferable to use a rinse solution containing at least one organic solvent selected from the group consisting of hydrocarbon-based solvents, ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, and ether-based solvents. Do. More preferably, after the developing step, the resist pattern is washed with a rinse solution containing at least one organic solvent selected from the group consisting of ketone-based solvents, ester-based solvents, alcohol-based solvents, and amide-based solvents. Process is performed. More preferably, after the developing step, a step of washing the resist pattern using a rinse liquid containing an alcohol-based solvent or an ester-based solvent is performed. Even more preferably, after the developing step, a step of washing the resist pattern using a rinse liquid containing a monohydric alcohol is performed. Particularly preferably, after the developing step, a step of washing the resist pattern using a rinse liquid containing a monohydric alcohol having 5 or more carbon atoms is performed. The time for washing the resist pattern is not particularly limited, but is preferably 10 seconds to 90 seconds.

Here, the monovalent alcohol used in the washing step after the developing step is not particularly limited, and examples thereof include straight chain, branched, and cyclic monovalent alcohols. Although it is not specifically limited, Specifically, for example, 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4 -Methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octan All, 4-octanol, etc. are mentioned, and monohydric alcohol with 5 or more carbon atoms is especially preferable. The monohydric alcohol having 5 or more carbon atoms is not particularly limited, and examples thereof include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, and 3-methyl-1-butanol. Can be lifted.

The rinse liquid may be mixed in plural, or may be used in combination with an organic solvent other than the above.

The water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting this water content to 10% by mass or less, better developing characteristics can be obtained.

The vapor pressure of the rinse liquid used in the washing step after the developing step is preferably 0.05 kPa or more and 5 kPa or less at 20 ° C, more preferably 0.1 kPa or more and 5 kPa or less, and even more preferably 0.12 kPa or more and 3 kPa or less. . By setting the vapor pressure of the rinse liquid to be 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is further improved, furthermore, swelling due to the penetration of the rinse liquid is further suppressed, and the dimensional uniformity in the wafer surface is further improved. .

An appropriate amount of surfactant may be added to the rinse solution and used.

In the cleaning step, the developed wafer is cleaned by using a rinse solution containing the organic solvent described above. The method of the cleaning treatment is not particularly limited, for example, a method of continuously drawing a rinse liquid on a substrate rotating at a constant speed (rotation coating method), a method of immersing a substrate in a bath filled with a rinse liquid for a certain period of time ( Dip method), a method of spraying a rinse liquid on the surface of the substrate (spray method), and the like can be applied. Among these, cleaning treatment is performed by a rotational coating method, and after cleaning, the substrate is rotated at a rotational speed of 2000 rpm to 4000 rpm, and then rinsed. It is preferred to remove the liquid from the substrate.

After the resist pattern is produced, the pattern wiring substrate is obtained by etching. The etching method is not particularly limited, and for example, known methods such as dry etching using plasma gas and wet etching using an alkali solution, cupric chloride solution, ferric chloride solution, or the like can be used.

After the resist pattern is produced, plating may be performed thereon. Although it does not specifically limit as said plating method, For example, copper plating, solder plating, nickel plating, gold plating, etc. are mentioned.

The remaining resist pattern after etching can be peeled off with an organic solvent. Although it does not specifically limit as said organic solvent, For example, PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), EL (ethyl lactate), etc. are mentioned. Although it does not specifically limit as said peeling method, For example, an immersion method, a spray method, etc. are mentioned. Further, the wiring board on which the resist pattern is formed may be a multilayer wiring board or may have a small diameter through hole.

The wiring substrate may be produced by a method of manufacturing a resist pattern, depositing a metal in a vacuum, and then dissolving the resist pattern with a solution, that is, a lift-off method.

Example

Hereinafter, embodiments of the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to these examples. In the following synthesis examples, the structure of the compound was confirmed by ¹ H-NMR measurement.

<Synthesis Example 1> Synthesis of (cct) body of calixresorcinarene derivative

To an autoclave (manufactured by SUS316L) with an electronic stirring device having a volume of 500 ml that can control the temperature, 74.3 g (3.71 mol) of anhydrous HF and 50.5 g (0.744 mol) of BF ₃ were added. In the autoclave, the contents were stirred and the pressure was raised to 2 MPa with carbon monoxide while maintaining the liquid temperature at -30 ° C. Subsequently, in the autoclave, a raw material in which 57.0 g (0.248 mol) of 4-cyclohexylbenzene and 50.0 g of n-heptane was mixed was supplied while maintaining the pressure at 2 MPa and the liquid temperature at -30 ° C, and then 1 hour. Maintained. Thereafter, the contents of the autoclave were poured into ice, diluted with benzene, and neutralized to collect an oil layer. As a result of obtaining the reactivity by analyzing the obtained oil layer by gas chromatography, the 4-cyclohexylbenzene conversion rate was 100% and the 4-cyclohexylbenzaldehyde selectivity was 97.3%.

The target component was isolated from the oil layer by monodistillation and analyzed by gas chromatography mass spectrometry (GC-MS). As a result, the isolated material showed a molecular weight of 188 of 4-cyclohexylbenzaldehyde (hereinafter also referred to as "CHBAL") of the target product. In addition, ¹ H-NMR in a heavy chloroform solvent was measured for the isolate. The chemical shift values of ¹ H-NMR (δppm, based on TMS) are 1.0 to 1.6 (m, 10H), 2.6 (m, 1H), 7.4 (d, 2H), 7.8 (d, 2H), and 10.0 (s) , 1H).

[Formula 40]

Resorcinol (16.5 g, 0.15, manufactured by Kanto Chemical Co., Inc.) under a nitrogen stream in a four-neck flask (500 mL) equipped with a sufficiently dry, nitrogen-substituted dropping funnel, a dimrose cooling tube, a thermometer, and a stirring blade. mol) and ethanol (255 g) were added to prepare an ethanol solution. The ethanol solution was ice-cooled and cooled and stirred at 5 to 15 ° C. To this ethanol solution, concentrated sulfuric acid (97%, 13.9g, 0.15mol) and pure water (17.9g) were added dropwise over 10 minutes using a dropping funnel. Then, further, 4-cyclohexylbenzaldehyde (29.7 g, 0.16 mol) obtained above and ethanol (26 g) were added dropwise to obtain a mixed solution. Thereafter, the obtained mixed solution was heated to 40 ° C with a mantle heater and stirred for 5 hours to react. After completion of the reaction, the obtained reaction solution was allowed to cool to room temperature, and then cooled in an ice bath. To the reaction solution after cooling, 1 L of ethyl acetate was added to prepare a uniform solution. Thereafter, the homogeneous solution was washed three times with 200 mL of pure water and twice with saturated brine. Water was removed from the solution after washing with magnesium sulfate, and ethyl acetate was distilled off to obtain a reaction product. The reaction was dried under vacuum at 40 ° C. to obtain 38.3 g of product (hereinafter also referred to as “CR-1a”).

This product (CR-1a) was analyzed by high speed liquid chromatography (HPLC). As a result, in the obtained CR-1a, the composition ratio of the (ccc) body / (ctt) body / (cct) body / (tct) body was 18.5 / 10.1 / 71.4 / 0.0.

450 mL of methanol was added to this product (CR-1a) to obtain a solution containing insoluble matter. The insoluble matter and the solution were separated by filtration. The obtained filtrate was concentrated to obtain 35 g of concentrate. Furthermore, ethyl acetate: hexane = 100 mL: 100 mL was added to the obtained concentrate to obtain a solution containing an insoluble matter. The insoluble matter and the solution were separated by filtration. The obtained filtrate was filled with 500 g of silica gel, and a mixed solution of ethyl acetate: hexane = 1/1/1/0 was developed to concentrate 9.9 g of the concentrate (hereinafter also referred to as "CR-1b"). Got

This concentrate (CR-1b) was analyzed by high speed liquid chromatography (HPLC). As a result, in the obtained CR-1b, the composition ratio of the (ccc) body / (ctt) body / (cct) body / (tct) body was 3.7 / 2.6 / 93.7 / 0.0.

In addition, the main component of CR-1b was analyzed by gel permeation chromatography (GPC). As a result, in the main component of the obtained CR-1b, the number average molecular weight (Mn) in terms of styrene was 979, and weight average molecular weight (Mw) was 986. In addition, ¹ H-NMR in a medium acetonitrile solvent was measured for the main component of CR-1b. The chemical shift values of this ¹ H-NMR (δppm, based on TMS) are 0.8 to 1.9 (m, 44H), 5.6, 5.7, 5.7 (m, 4H), 6.2 to 6.5 (d, 8H), and 6.5 to 7.0 (m) , 16H), 7.1 (m, 8H).

From these results, it was identified that the main component of the obtained CR-1b was (cct) isomer.

[Formula 41]

((cct) isomer)

<Synthesis Example 2> Synthesis of (ctt) body of calix resorcinane derivative

Resorcinol (23.1 g, 0.2, manufactured by Kanto Chemical Co., Inc.) in a four-necked flask (500 mL) with a sufficiently dry, nitrogen-substituted dropping funnel, Dimrose cooling tube, thermometer, and stirring vane. mol) and ethanol (190 g) were added to prepare an ethanol solution. The ethanol solution was ice-cooled and cooled and stirred at 5 to 15 ° C. To this ethanol solution, concentrated sulfuric acid (97%, 18.5g, 0.2mol) and pure water (23.9g) were added dropwise over 10 minutes by a dropping funnel. Then, further, 4-cyclohexyl benzaldehyde (37.7 g, 0.2 mol) and ethanol (21 g) obtained above were added dropwise to obtain a mixed solution. Then, the obtained mixed solution was heated to 80 ° C with a mantle heater and stirred for 5 hours to react. After completion of the reaction, the obtained reaction solution was allowed to cool to room temperature, and then cooled in an ice bath. After cooling, the reaction solution was allowed to stand for 1 hour, and the resulting pale yellow target crystals were filtered and separated. The crude crystals were washed 3 times with 500 mL of methanol and 5 times with 500 mL of pure water. The solid content was filtered and vacuum dried from the solution after washing to obtain 42.5 g of product (hereinafter also referred to as "CR-2a").

This product (CR-2a) was analyzed by high-speed liquid chromatography (hereinafter also referred to as "HPLC"). As a result, in the obtained CR-2a, the composition ratio of the (ccc) body / (ctt) body / (cct) body / (tct) body was 49.9 / 49.9 / 0.2 / 0.0.

40 g of this product (CR-2a) was recrystallized twice with a mixed solution of tetrahydrofuran 8L / hexane 8L. 11 g of the filtrate concentrate obtained from the second recrystallization was subjected to the third recrystallization with 100 mL of ethyl acetate to obtain 9 g of a crystal ((hereinafter also referred to as "CR-2b")) containing a lot of (ctt) isomers.

This crystal (CR-2b) was analyzed by HPLC. As a result, in the obtained CR-2b, the composition ratio of the (ccc) body / (ctt) body / (cct) body / (tct) body was 3.1 / 96.9 / 0.0 / 0.0.

In addition, the main component of CR-2b was analyzed by GPC. As a result, in the main component of the obtained CR-2b, the number average molecular weight (Mn) in terms of styrene was 979, and weight average molecular weight (Mw) was 986. In addition, ¹ H-NMR in a medium acetonitrile solvent was measured for the main component of CR-2b. Chemical shift values (δppm, based on TMS) of this ¹ H-NMR are 0.8 to 1.9 (m, 44H), 5.5 (s, 4H), 6.0 to 6.4 (d, 8H), 6.6 to 6.7 (m, 16H), 8.4,8.5 (m, 8H).

From these results, it was identified that the main component of the obtained CR-2b is (ctt) isomer.

[Formula 42]

((cct) isomer)

<Synthesis Example 3> Synthesis of (ccc) body of calixresorcinarene derivative

In Synthesis Example 2, 22 g of the crystal obtained from the second recrystallization of CR-2a was subjected to the third recrystallization with 800 mL of ethyl acetate, and (ccc) a crystal containing a lot of isomers (hereinafter referred to as "CR-3a") Also called) 10 g was obtained. This crystal (CR-3a) was analyzed by HPLC. As a result, in the obtained CR-3a, the composition ratio of the (ccc) body / (ctt) body / (cct) body / (tct) body was 97.6 / 2.4 / 0.0 / 0.0.

In addition, the main component of CR-3a was analyzed by GPC. As a result, in the main component of the obtained CR-3a, the number average molecular weight (Mn) in terms of styrene was 979, and weight average molecular weight (Mw) was 986. In addition, ¹ H-NMR in a medium acetonitrile solvent was measured for the main component of CR-3a. The chemical shift value of this ¹ H-NMR (δppm, based on TMS) is 0.8 to 1.9 (m, 44H), 5.6 (s, 4H), 6.1 to 6.5 (d, 8H), 6.7 to 6.9 (m, 16H), 8.5 (m, 8H).

From these results, it was identified that the main component of the obtained CR-3a is (ccc) isomer.

[Formula 43]

((cct) isomer)

<Examples 1 to 6 and Comparative Examples 1 to 3>

(1) Preparation of resist composition

As described in Table 1, each component was combined to obtain a uniform solution. Then, the obtained homogeneous solution was filtered through a membrane filter made of 0.1 μm n TEFLON (registered trademark) with a pore diameter to prepare a resist composition. The following evaluation was performed about each prepared resist composition. The evaluation results are shown in Table 2.

"P-1", "C-1", "Q-1", and "S-1" in Table 1 are as follows, respectively.

Acid generator (C)

P-1: Triphenylbenzenesulfonium trifluoromethanesulfonate (Midori Kagaku Co., Ltd.)

Acid crosslinking agent (G)

C-1: NIKALAC MW-100LM (Sanwa Chemical Industrial Co., Ltd.)

Acid diffusion control agent (E)

Q-1: Trioctylamine (Tokyo Chemical Industry Co., Ltd.)

menstruum

S-1: Propylene glycol monomethyl ether (Tokyo Chemical Industry Co., Ltd.)

(2) Patterning test

The resist composition obtained in (1) was rotated (spin coated) on a clean silicon wafer, and then baked (PB) in an oven at 110 ° C. to form a resist film (amorphous film) having a thickness of 40 nm. The electron beam of the following three types of pattern setting was irradiated to this resist film using an electron beam drawing apparatus (ELS-7500, manufactured by Elionix Inc.).

Pattern 1: 50nm linear exposure section and 50nm linear unexposed section repeat pattern

Pattern 2: 40 nm linear exposure section and 40 nm linear unexposed section repeat pattern

Pattern 3: Repeated pattern of 30nm linear exposure section and 30nm linear unexposed section

After this irradiation, the resist film was heated at a predetermined temperature (110 ° C.) for 90 seconds, respectively, and then developed by immersing it in a 2.38% by mass alkali developer solution of tetramethyl ammonium hydrooxide (TMAH) for 60 seconds. Thereafter, the resist film was washed with ultrapure water for 30 seconds and dried to form a negative resist pattern.

The line and space in the obtained resist pattern was observed with a scanning electron microscope (S-4800 manufactured by Hitachi High-Technologies Corporation). In addition, the dose amount at that time (μC / cm ² ) was taken as the sensitivity and evaluated as follows.

(Evaluation criteria for sensitivity)

1 (excellent sensitivity): dose amount ≤ 45 μC / cm ²

2 (good sensitivity): 45 μC / cm ² <dose amount ≤ 60 μC / cm ²

3 (defective sensitivity): 60 μC / cm ² <dose amount

The line edge roughness (hereinafter also referred to as "LER") of the obtained resist pattern was measured as follows. At any 300 points in the longitudinal direction (0.75 μm) of the 1: 1 line and space of the obtained resist pattern, Hitachi, Ltd. Using an SEM terminal PC V5 off-line measuring software for semiconductors (manufactured by Hitachi High-Tech Science Corporation), the distance between the edge and the reference was measured, and a standard deviation (3σ) was calculated from the measurement results to be LER.

〔LER's evaluation criteria〕

A (excellent LER): LER≤5.0nm

B (good LER): 5.0nm <LER≤10.0nm

C (poor LER): 10.0nm <LER (contains a collapsed pattern)

D: No pattern

From the evaluation results, it was confirmed that the resist composition obtained in this example had better sensitivity and LER than the resist composition obtained in the comparative example.

As described above, it has been found that a resist composition containing a resist substrate containing a specific stereoisomer as a main component is highly sensitive, has a small roughness, and can form a resist pattern having a good shape. As long as the above-mentioned requirements of the present embodiment are satisfied, the same effect is obtained when compounds other than those described in the examples are used.

Industrial availability

The resist composition containing a specific amount of the specific stereoisomer of the present invention is useful as a resist material, particularly an acid-amplified low molecular weight resist material, and is suitably used in a resist pattern forming method.

Claims (17)

In the resist composition comprising a resist substrate and a solvent,
A resist composition in which the resist substrate contains a compound represented by the following formula (1), and the proportion of the compound represented by the following formula (1) to the resist substrate is 50 to 100% by mass.

(In formula (1), R is each independently a hydrogen atom, a substituted or unsubstituted heterocyclic group, a halogen atom, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted 3 to 20 carbon atoms. Branched aliphatic hydrocarbon group, substituted or unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, substituted or unsubstituted aryl group having 6 to 20 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, substituted or unsubstituted carbon number 1 to 20 alkoxy groups, substituted or unsubstituted amino groups having 0 to 20 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted acyl groups having 1 to 20 carbon atoms, substituted or unsubstituted 2 to 20 carbon atoms An alkoxycarbonyl group, a substituted or unsubstituted alkylloyloxy group having 1 to 20 carbon atoms, a substituted or unsubstituted arylloyloxy group having 7 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 20 carbon atoms, or a divalent group of these groups A group (one or more groups selected from the group consisting of substituted or unsubstituted alkylene groups, substituted or unsubstituted arylene groups, and ether groups);
R 'and X are each independently a hydrogen atom, a hydroxyl group, a cyano group, a nitro group, a substituted or unsubstituted heterocyclic group, a halogen atom, or a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, substituted or unsubstituted Branched aliphatic hydrocarbon group having 3 to 20 carbon atoms, substituted or unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, substituted or unsubstituted aryl group having 6 to 20 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, substitution Or an unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted amino group having 0 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted acyl group having 1 to 20 carbon atoms, a substituted or unsubstituted group, An alkoxycarbonyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkylloyloxy group having 1 to 20 carbon atoms, a substituted or unsubstituted arylloyloxy group having 7 to 20 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 20 carbon atoms, or A group in which these groups and a divalent group (one or more groups selected from the group consisting of substituted or unsubstituted alkylene groups, substituted or unsubstituted arylene groups, and ether groups) are bonded,
Also, in the plane of the 16-membered ring, the directions of the other three R 'relative to the direction of one R' are the directions of the cis-cis-trans in clockwise order.)
According to claim 1,
In the formula (1), X is a hydrogen atom, a hydroxyl group, or a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms.
According to claim 1,
In the above formula (1), R 'is a group represented by the following formula (2), and X is a hydrogen atom.

(In formula (2), p is an integer from 0 to 4,
R ¹² is each independently a cyano group, a nitro group, a halogen atom, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 14 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 14 carbon atoms, substituted or unsubstituted, A cyclic aliphatic hydrocarbon group having 3 to 14 carbon atoms, or a group represented by the following formula (3),

In the formula (3), R ⁴ is each independently a cyano group, a nitro group, a substituted or unsubstituted heterocyclic group, a halogen atom, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 14 carbon atoms, a substituted or unsubstituted carbon number. 3 to 14 branched aliphatic hydrocarbon groups, substituted or unsubstituted cyclic aliphatic hydrocarbon groups having 3 to 14 carbon atoms, substituted or unsubstituted aryl groups having 6 to 14 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 14 carbon atoms, or substituted or It is an unsubstituted alkylsilyl group having 1 to 14 carbon atoms, and q is an integer from 0 to 5.)
According to claim 1,
In the above formula (1), R 'is a group represented by the following formula (4), and R and X are hydrogen atoms.

The method according to any one of claims 1 to 4,
A resist composition having a content of 20 to 99% by mass of the solvent, and a content of 1 to 80% by mass of components other than the solvent.
The method according to any one of claims 1 to 4,
Acid generator (C) that directly or indirectly generates acid by irradiation of any one radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet (EUV), X-ray and ion beam Resist composition further comprising a.
The method according to any one of claims 1 to 4,
A resist composition further comprising an acid crosslinking agent (G).
The method according to any one of claims 1 to 4,
A resist composition further comprising an acid diffusion controlling agent (E).
The method according to any one of claims 1 to 4,
Components other than the solvent include the resist substrate (A), an acid generator (C), an acid crosslinking agent (G), and an acid diffusion control agent (E),
The content of the resist base material (A) is 50.000 to 99.498 parts by mass, the content of the acid generator (C) is 0.001 to 49.000 parts by mass, and the acid crosslinking agent (G) relative to the total content of 100 parts by mass of the components other than the above-mentioned solvent The content of the resist composition is 0.500 to 49.000 parts by mass, and the content of the acid diffusion control agent (E) is 0.001 to 49.000 parts by mass.
According to claim 1,
A resist composition capable of forming an amorphous film by spin coating.
The method of claim 10,
A resist composition having a dissolution rate of the amorphous film in a developer at 23 ° C. of 10 MPa / sec or higher.
The method of claim 10,
KrF excimer laser, extreme ultraviolet, electron, or X-ray irradiation of the amorphous film, or, after heating at 20 ~ 250 ℃, the amorphous film, the dissolution rate of the developer in the resist composition is 5Å / sec or less.
A process of applying the resist composition according to any one of claims 1 to 4 onto a substrate and forming a resist film,
A step of exposing the resist film,
Process for developing the exposed resist film,
Method of manufacturing a resist pattern comprising a.
delete delete delete delete